Name: 41233-93-6|Potassium 2-methylbutan-2-olate|98%
Brand: Ambeed
SKU: A201641
Rating: 93 (27 reviews)

1
[ 354-58-5 ]
[ 41233-93-6 ]
2-(2,2-Dichloro-1,1-difluoro-ethoxy)-2-methyl-butane [ No CAS ]
[ 98481-73-3 ]

Reference： [1]Angewandte Chemie,1985,vol. 97,p. 867 - 868

2
[ 76-11-9 ]
[ 41233-93-6 ]
2-(2,2-Dichloro-1,1-difluoro-ethoxy)-2-methyl-butane [ No CAS ]
[ 98481-73-3 ]

Reference： [1]Angewandte Chemie,1985,vol. 97,p. 867 - 868

3
[ 76-13-1 ]
[ 41233-93-6 ]
2-(2-Chloro-1,1,2-trifluoro-ethoxy)-2-methyl-butane [ No CAS ]
[ 98481-69-7 ]

Reference： [1]Angewandte Chemie,1985,vol. 97,p. 867 - 868

4
[ 41233-93-6 ]
[ 13067-81-7 ]
[ 108-88-3 ]
[ 589-81-1 ]
[ 2785-29-7 ]
lithium 2-methylbutan-2-olate [ No CAS ]

Reference： [1]Journal of Organometallic Chemistry,1987,vol. 326,p. 1 - 8

5
[ 41233-93-6 ]
[ 75343-42-9 ]
2,6-diphenyl-3-vinylpyridine [ No CAS ]

Reference： [1]Acta Crystallographica, Section C: Crystal Structure Communications,1995,vol. 51,p. 525 - 527

6
[ 75-85-4 ]
[ 41233-93-6 ]

Reference： [1]Dalton Transactions,2018,vol. 47,p. 12582 - 12586
[2]Synthesis,1995,p. 1493 - 1495

7
[ 41233-93-6 ]
[ 25662-24-2 ]
[ 188818-06-6 ]
1-Benzyl-2-(1,1-dimethyl-propoxymethyl)-aziridine [ No CAS ]

Reference： [1]Journal of Organic Chemistry,1997,vol. 62,p. 2448 - 2452

8
[ 98-87-3 ]
[ 41233-93-6 ]
benzaldehyde di-t-pentyl acetal [ No CAS ]

Reference： [1]Journal of Organic Chemistry,2003,vol. 68,p. 706 - 717

9
[ 131-11-3 ]
[ 41233-93-6 ]
di-tert-amyl phthalate [ No CAS ]

Reference： [1]Macromolecules,2005,vol. 38,p. 7684 - 7694

11
[ 41233-93-6 ]
[ 100-06-1 ]
[ 105-58-8 ]
[ 2881-83-6 ]

Yield	Reaction Conditions	Operation in experiment
	With acetic acid; In water; toluene;	Example 15B Ethyl (4-methoxybenzoyl)acetate To potassium t-amylate (25 wt %, 50.8 kg, 99.26 mol) in toluene (15.2 kg) cooled to 5 C. under mechanical stirring and under nitrogen was added a mixture of 4-methoxyacetophenone (6.755 kg, 44.98 mol) and diethyl carbonate (6.40 kg, 54.18 mol) in toluene over 1 hour maintaining the temperature below 10 C. The reaction mixture was heated to 60 C. for 8 hours until no 4-methoxyacetophenone was detected by HPLC. The mixture was cooled to 20 C. and quenched by adding to a mixture of acetic acid (8 kg) and water (90 kg) over 30 minutes while maintaining the temperature at <20 C. The layers were separated, and the organic layer was washed with 5% sodium bicarbonate solution (41 kg) and concentrated to 14.65 kg. The temperature is maintained below 50 C. during the distillation. The yellow product concentrate was assayed by HPLC against an external standard and the yield was found to be 9.40 kg (94%).
		A mixture of potassium tert-amylate (50.8 Kg) in toluene (15.2 Kg) at 5 C. was treated with 4-methoxyacetophenone (6.755 Kg) and diethyl carbonate (6.4 Kg) in toluene over 1 hour while keeping the solution temperature below 110 C., warmed to 60 C. for 8 hours, cooled to 20 C. and treated with acetic acid (8 Kg) and water (90 Kg) over 30 minutes while keeping the solution temperature below 20 C. The organic layer was isolated, washed with 5% aqueous sodium bicarbonate (41 Kg) and concentrated at 50 C. to 14.65 Kg.

Reference： [1]Patent: US6124341,2000,A
[2]Patent: US2006/63825,2006,A1 .Location in patent: Page/Page column 9

12
[ 362-08-3 ]
[ 1779-49-3 ]
[ 41233-93-6 ]
[ 431901-73-4 ]

Yield	Reaction Conditions	Operation in experiment
	In benzene;	EXAMPLE 31 17(20)-methyleneestra-1,3,5(10)-triene-3-ol (Table 1, Entry 10) Representative procedure for preparation of 17-olefin-2-methoxyestrone analogs: Potassium-tert-amylate (1.54 M, toluene, 4.35 mL 6.69 mmol, prepared as in Schow et al J. Org. Chem. 1979, 44, 3760) was added to a suspension of methyl triphenylphosphonium bromide (2.39 g, 6.69 mmol) in anhydrous benzene and refluxed for 30 min. 2-Methoxyestrone (300 mg, 1 mmol) in warm benzene (5 mL) was added and the mixture was refluxed for 3 h. The reaction was cooled to rt, poured into 100 mL water, washed with ether (2100 mL). The combined organics were washed with 6 M HCl (1100 mL), NaHCO3 (satd, 1100 mL), water (1100 mL), and brine (1*100 mL). Dry with sodium sulfate, filter and rotoevap to give a semi solid-yellowish oil. Purify by silica gel column chromatography using 95:5 chloroform:methanol as an eluent.

Reference： [1]Patent: US2002/82433,2002,A1

13
[ 75-85-4 ]
[ 78-79-5 ]
[ 41233-93-6 ]

Yield	Reaction Conditions	Operation in experiment
	In hexane;	25.3 g (648 mmol) of purified potassium crusts (Merck) were melted in 305 g hexane in a 0.5-1 twice clad reactor with a precision glass stirrer, reflux condenser and drip funnel, and then a mixture of 57.1 g (648 mmol) tert-amyl alcohol and 22.1 g (324 mmol) isoprene was added thereto at approximately 60 C. within 100 minutes. During the addition process, the reaction mixture became slightly cloudy, although was easy to stir. At the end of the addition, refluxing was effected for 10 minutes, with a clear, slightly yellowish solution being formed. The filtered solution was concentrated by evaporation in a rotation evaporator under vacuum. 74.8 g (92%) of a colourless powder was obtained that had the expected composition for PTA.

Reference： [1]Patent: US6294705,2001,B1

14
[ 41233-93-6 ]
[ 90319-52-1 ]
[ 451-81-0 ]
[ 216754-32-4 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium chloride; In water; toluene;	A solution of 46.0 g of (R)-4-phenyl-2-oxazolidinone in 300 g (338 mL) of peroxide-free tetrahydrofuran is cooled to -5 to 0 C. (bath temperature -10 to -5 C.) over a period of 15 minutes. 145.2 g (166.8 mL) of 25% w/w potassium t-amylate/toluene solution is added over a period of 25 minutes while maintaining an internal temperature below 0 C. The reaction mixture is warmed to 20+-5 C. within 1 hour and stirred at this temperature for 2.5-3 hours. The mixture is cooled to -15 to -5 C. over a period of 30 minutes, and crude 2-fluorobenzenacetyl chloride (obtained above) is added over a period of 45 minutes while maintaining an internal temperature below -5 C. (bath temperature -15 to -10 C.). After the addition is completed, the mixture is warmed to 20+-5 C. over a period of 1 hour, and diluted with 100 mL of toluene. This is added to 500 mL of saturated citric acid monosodium salt solution (100 g in 450 g of water) and the mixture is stirred for 5 minutes. The organic layer is separated, and washed with 1 L of sodium chloride solution (200 g in 800 g of water) in two equal portions of 500 mL each. The solution is concentrated to dryness under reduced pressure (66-76 mm Hg, bath temperature 65-70 C.) to obtain 3-[2-(2-fluorophenyl)-1-oxoethyl]-4(R)-phenyl-2-oxazolidinone as a semi-solid.

Reference： [1]Patent: US6174888,2001,B1

15
[ 41233-93-6 ]
[ 100-06-1 ]
[ 105-58-8 ]
[ 83511-12-0 ]

Yield	Reaction Conditions	Operation in experiment
	With acetic acid; In water; toluene;	4-Methoxybenzoyl acetate To potassium t-amylate (25 wt %, 50.8 kg, 99.26 mol) in toluene (15.2 kg) cooled to 5 C. under mechanical stirring and under nitrogen was added a mixture of 4-methoxyacetophenone (6.755 kg, 44.98 mol) and diethyl carbonate (6.40 kg, 54.18 mol) in toluene over 1 hour maintaining the temperature below 10 C. The reaction mixture was heated to 60 C. for 8 hours until no 4-methoxyacetophenone was detected by HPLC. The mixture was cooled to 20 C. and quenched by adding to a mixture of acetic acid (8 kg) and water (90 kg) over 30 minutes while maintaining the temperature at <20 C. The layers were separated, and the organic layer was washed with 5% sodium bicarbonate solution (41 kg) and concentrated to 14.65 kg. The temperature is maintained below 50 C. during the distillation. The yellow product concentrate was assayed by HPLC against an external standard and the yield was found to be 9.40 kg (94%).

Reference： [1]Patent: US6162927,2000,A

16
[4aR-(4aα,5β,8β,8aβ)]-octahydro-5,8-epoxy-1H-2-benzopyran-3-ol [ No CAS ]
[ 6399-81-1 ]
[ 41233-93-6 ]
[1S-[1α,2α(Z),3α,4α]]-6-[3-hydroxymethyl)-7-oxabicyclo[2.2.1]hept-2-yl]-4-hexenoic acid [ No CAS ]
[ 791-28-6 ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; sodium chloride; In tetrahydrofuran; water; potassium carbonate; acetic acid; ethyl acetate; toluene;	C. [1S-[1alpha,2alpha(Z),3alpha,4alpha]]-6-[3-(Hydroxymethyl)-7-oxabicyclo[2.2.1]hept-2-yl]-4-hexenoic acid, methyl ester To a partial solution of 36.27 g of [4aR-(4aalpha,5beta,8beta,8abeta)]-octahydro-5,8-epoxy-1H-2-benzopyran-3-ol (prepared as described in U.S. Pat. No. 4,143,054) (0.23 mol) and 3-carboxypropyltriphenylphosphonium bromide (127.34 g, 0.37 mol) in 600 mL of dry THF under argon at 3 C. was added dropwise over 1 hour a solution of 370.6 mL of potassium t-amylate (0.68 mol of a 1.8M toluene solution) with mechanical stirring. Initially the reaction temperature reached a maximum of 8 C. and subsequently leveled off to 4 C. for the remainder of the base addition. The reaction was then run at room temperature for 90 minutes. A 0 C. ice bath was introduced and the reaction was quenched by the addition of 152 mL of glacial acetic acid, over 30 minutes. Solvents were removed in vacuo (azeotroped with toluene). Water (640 mL) and 50 mL of concentrated HCl were added (pH 2.6). Dilution with 640 mL of ethyl acetate, the addition of 149 g of NaCl and a few seed crystals of 3-carboxypropyltriphenylphosphonium bromide was followed by vigorous stirring for 15 minutes. The precipitate was collected by filtration and washed with 2 portions each of 320 mL of ethyl acetate. The ethyl acetate layer was separated, the aqueous layer was extracted with ethyl acetate (2200 mL each), the combined ethyl acetate layers were dried over MgSO4 and concentrated. Aqueous 5% K2 CO3 was added (507 mL) followed by vigorous stirring for 1 hour. No precipitation occurred. The reaction mixture was concentrated to a paste and suspended in 508 mL of water. Several hours of vigorous stirring produced no precipitate. The water was decanted off and the residue was suspended in 200 mL of aqueous 5% K2 CO3 solution. After vigorous stirring, a light tan solid was collected by filtration and rinsed several times with water. The combined aqueous layers were extracted 5 with 1:1 toluene/ether (230 mL each). After cooling the combined aqueous layers with a 0 C. ice bath, concentrated HCl was added to pH 2.5, followed by extraction 1* with 460 mL then 2* with 230 mL each of ethyl acetate. The combined ethyl acetate layers were dried over MgSO4 and evaporated in vacuo to yield 49.74 of an amber oil. Trituration from 330 mL of ether (room temperature, overnight) oiled out phosphorous by-products. The ether solution was decanted away from the dark red oil into a separatory funnel, and the oil which was carried over by the decantation was drained off (1.56 g). Evaporation of the ether solution in vacuo yielded 43.08 g of [1S-[1alpha,2alpha(Z),3alpha,4alpha]]-6-[3-hydroxymethyl)-7-oxabicyclo[2.2.1]hept-2-yl]-4-hexenoic acid in the form of a viscous yellow oil. 1 H NMR indicated a product: triphenylphosphine oxide: ether molar ratio of 23:1:1.8 (mass % 93:4.7:2.2). Yield exclusive of triphenylphosphine oxide/ether, 40.06 g (72.5%).

Reference： [1]Patent: US5290799,1994,A

17
[ 111-88-6 ]
[ 61167-58-6 ]
[ 41233-93-6 ]
[ 179948-13-1 ]

Yield	Reaction Conditions	Operation in experiment
	In toluene;	a) Preparation of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenylmethyl)-4-methylphenyl 3-(octylthio)propanoate In a 200 ml sulfonation flask, 9.86 g (25 mmol) of 2,2'-methylenebis[6-tert-butyl-4-methylphenol]monoacrylate and 4.02 g (27.5 mmol) of octanethiol are dissolved in 50 ml of toluene. Then 0.75 ml (1.25 mmol) of a 1.7N solution of potassium tert-pentylate in toluene is added dropwise at RT. Afterwards the reaction mixture is heated to c. 55 C. and stirred for 1 hour at this temperature. The mixture is cooled to RT and poured into dilute hydrochloric acid (0.1N). After repeated extraction with ethyl acetate the organic phases are combined, dried over sodium sulfate and concentrated on a vacuum rotary evaporator. Unreacted bisphenol is removed (bulb tube distillation at 200 C./10 mbar), giving 11.35 g (84%) of the desired compound as a pale yellow oil.

Reference： [1]Patent: US5602196,1997,A

18
4aR-(4aα,5β,8β,8aβ)]-octahydro-5,8-epoxy-1H-2 -benzopyran-3-ol [ No CAS ]
[ 41233-93-6 ]
[ 17857-14-6 ]
[1S-[1α,2α(Z),3α,4α]]-6-[3-hydroxymethyl)-7-oxabicyclo[2.2.1]hept-2 -yl]-4-hexenoic acid [ No CAS ]
[ 791-28-6 ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; sodium chloride; In tetrahydrofuran; water; potassium carbonate; acetic acid; ethyl acetate; toluene;	C. 1S-[1alpha,2alpha(Z),3alpha,4alpha]]-6-[3-(Hydroxy-methyl)-7-oxabicyclo[2.2.1]hept-2 -yl]-4-hexenoic acid, methyl ester To a partial solution of 36.27 g of 4aR-(4aalpha,5beta,8beta,8abeta)]-octahydro-5,8-epoxy-1H-2 -benzopyran-3-ol (prepared as described in U.S. Pat. No. 4,143,054) (0.23 mol) and 3-carboxypropyl-triphenylphosphonium bromide (127.34 g, 0.37 mol) in 600 mL of dry THF under argon at 3 C. was added dropwise over 1 hour a solution of 370.6 mL of potassium t-amylate (0.68 mol of a 1.8M toluene solution) with mechanical stirring. Initially the reaction temperature reached a maximum of 8 C. and subsequently leveled off to 4 C. for the remainder of the base addition. The reaction was then run at room temperature for 90 minutes. A 0 C. ice bath was introduced and the reaction was quenched by the addition of 152 mL of glacial acetic acid, over 30 minutes. Solvents were removed in vacuo (azeotroped with toluene). Water (640 mL) and 50 mL of concentrated HCl were added (pH 2.6). Dilution with 640 mL of ethyl acetate, the addition of 149 g of NaCl and a few seed crystals of 3-carboxypropyltriphenylphosphonium bromide was followed by vigorous stirring for 15 minutes. The precipitate was collected by filtration and washed with 2 portions each of 320 mL of ethyl acetate. The ethyl acetate layer was separated, the aqueous layer was extracted with ethyl acetate (2200 mL each), the combined ethyl acetate layers were dried over MgSO and concentrated. Aqueous 5% K2 CO3 was added (507 mL) followed by vigorous stirring for 1 hour. No precipitation occurred. The reaction mixture was concentrated to a paste and suspended in 508 mL of water. Several hours of vigorous stirring produced no precipitate. The water was decanted off and the residue was suspended in 200 mL of aqueous 5% K2 CO3 solution. After vigorous stirring, a light tan solid was collected by filtration and rinsed several times with water. The combined aqueous layers were extracted 5with 1:1 toluene/ether (230 mL each). After cooling the combined aqueous layers with a 0 C. ice bath, concentrated HCl was added to pH 2.5, followed by extraction 1 with 460 mL then 2with 230 mL each of ethyl acetate. The combined ethyl acetate layers were dried over MgSO4 and evaporated in vacuo to yield 49.74 of an amber oil. Trituration from 330 mL of ether (room temperature, overnight) oiled out phosphorous by-products. The ether solution was decanted away from the dark red oil into a separatory funnel, and the oil which was carried over by the decantation was drained off (1.56 g). Evaporation of the ether solution in vacuo yielded 43.08 g of [1S-[1alpha,2alpha(Z),3alpha,4alpha]]-6-[3-hydroxymethyl)-7-oxabicyclo[2.2.1]hept-2 -yl]-4-hexenoic acid in the form of a viscous yellow oil. 1 H NMR indicated a product: triphenylphosphine oxide: ether molar ratio of 23:1:1.8 (mass % 93:4.7:2.2). Yield exclusive of triphenylphosphine oxide/ether, 40.06 g (72.5%).

Reference： [1]Patent: US5100889,1992,A

19
[ 41233-93-6 ]
[ 71884-49-6 ]
[1β,2α(5Z),3α,4β]-7-[3-(2-Oxoethyl)-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With acetic acid; In toluene;	A. [1beta,2alpha(Z),3alpha,4beta]-7-[3-(2-Oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester Into a dry 100 ml round bottom 3-necked flask containing a stir bar was added dried 12.9 g (37.7 mmoles) methoxymethyltriphenylphosphonium chloride ((C6 H5)3 P+ --CH2 OCH3 Cl-) and 235 ml distilled toluene (stored over molecular sieves). The resulting suspension was stirred in an ice-bath, under argon, until cold and then a 1.55M solution of 18.3 ml (28.3 mmol) of potassium t-amylate in toluene was added dropwise. A bright red solution formed which was stirred at 0 C. for an additional 35 minutes. Thereafter, a solution of 4.97 g (18.8 mmol) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-formyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester in 60 ml toluene was added by means of a dropping funnel over a 35 minute period with the ice-bath still in place. The reaction was then quenched by addition of 2.3 g (39 mmol) acetic acid in 5 ml ether. The reaction mixture immediately turned pale yellow and was immediately poured into 200 ml saturated NH4 Cl, and extracted with ether (4*200 ml). The combined ether phases were washed with NaCl, saturated solution, and dried (MgSO4) and concentrated to yield a yellow oil in a white crystalline solid (phosphine oxide). The white solid was triturated with EtOAc and the mother liquor was purified by chromatography on an LPS-1 silica column. The fractions obtained were (A) [1beta,2alpha(Z),3alpha,4beta]-7-[3-(2-oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, (B) [1beta,2alpha(Z),3alpha,4beta]-7-[3-(2-methoxy)ethendiyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, and (C) [1beta,2alpha(Z),3alpha,4beta]-7-[3-(2,2-dimethoxy)ethyl-7-oxabicyclo[2.2.1]-hept-2-yl]-5-heptenoic acid, methyl ester.
	With acetic acid; In toluene;	A. [1beta,2alpha(5Z),3alpha,4beta]-7-[3-(2-Oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester Into a dry 100 ml round bottom 3-necked flask containing a stir bar was added 12.9 g (37.7 mmoles) methoxymethyltriphenylphosphonium chloride ((C6 H5)3 P+ --CH2 OCH3 Cl-) and 235 ml distilled toluene (stored over molecular sieves). The resulting suspension was stirred in an ice bath under argon, until cold and then a 1.55M solution of 18.3 ml (28.3 mmol) of potassium t-amylate in toluene was added dropwise. A bright red solution formed which was stirred at 0 C. for an additional 35 minutes. Thereafter, a solution of 4.97 g (18.8 mmol) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-formyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester in 60 ml toluene was added by means of a dropping funnel over a 35 minute period with the ice-bath still in place. The reaction was then quenched by addition of 2.3 g (39 mmol) acetic acid in 5 ml ether. The reaction mixture immediately turned pale yellow and was immediately poured into 200 ml saturated NH4 Cl and extracted with ether (4*200 ml). The combined ether phases were washed with NaCl, saturated solution, and dried (MgSO4) and concentrated to yield a yellow oil in a white crystalline solid (phosphine oxide). The white solid was triturated with EtOAc and purified by TLC on an LP-1 silica column. The fractions obtained were (A) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-(2-oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, (B) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-(2-methoxy)ethenyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, and (C) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-(2,2-dimethoxy)ethyl-7-oxabicyclo[2.2.1]hept-2-yl] -5-heptenoic acid, methyl ester.
	With acetic acid; In toluene;	A. [1beta,2alpha(5Z),3alpha,4beta]-7-[3-(2-Oxoethyl)-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester Into a dry 1000 ml round bottom 3-necked flask containing a stir bar was added dried 2.9 g (37.7 mmoles) methoxymethyltriphenylphosphonium chloride (C6 H5)3 P+ --CH2 OCH3 Cl-) and 235 ml distilled toluene (stored over molecular sieves). The resulting suspension was stirred in an ice bath, under argon, until cold and then a 1.55M solution of 18.3 ml (28.3 mmol) of potassium t-amylate in toluene was added dropwise. A bright red solution formed which was stirred at 0 C. for an additional 35 minutes. Thereafter, a solution of 4.97 g (18.8 mmol) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-formyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester in 60 ml toluene was added by means of a dropping funnel over a 35 minute period with the ice-bath still in place. The reaction was then quenched by addition of 2.3 g (39 mmol) acetic acid in 5 ml ether. The reaction mixture immediately turned pale yellow and was immediately poured into 200 ml saturated NH4 Cl and extracted with ether (4*200 ml). The combined ether phases were washed with NaCl, saturated solution, and dried (MgSO4) and concentrated to yield a yellow oil in a white crystalline solid (phosphine oxide). The white solid was triturated with EtOAc and purified by TLC on an LP-1 silica column. The fractions obtained were (A) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-(2-oxo)ethyl-7-oxabicyclo-[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, (B) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-(2-methoxy)ethendiyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, and (C) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-(2,2-dimethoxy)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester.

	With acetic acid; In toluene;	A. [1beta,2alpha(5Z),3alpha,4beta]-7-[3-(2-Oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester Into a dry 1000 ml round bottom 3-necked flask containing a stir bar was added dried 12.9 g (37.7 mmoles) methoxymethyltriphenylphosphonium chloride ((C6 H5)3 P+ --CH2 OCH3 Cl-) and 235 ml distilled toluene (stored over molecular sieves). The resulting suspension was stirred in an ice-bath, under argon, until cold and then a 1.55M solution of 18.3 ml (28.3 mmol) of potassium t-amylate in toluene was added dropwise. A bright red solution formed which was stirred at 0 C. for an additional 35 minutes. Thereafter, a solution of 4.97 g (18.8 mmol) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-formyl-7-oxabicyclo[2.2.1]-hept-2-yl]-5-heptenoic acid, methyl ester in 60 ml toluene was added by means of a dropping funnel over a 35 minute period with the ice-bath still in place. The reaction was then quenched by addition of 2.3 g (39 mmol) acetic acid in 5 ml ether. The reaction mixture immediately turned pale yellow and was immediately poured into 200 ml saturated NH4 Cl, and extracted with ether (4*200 ml). The combined ether phases were washed with NaCl, saturated solution, and dried (MgSO4) and concentrated to yield a yellow oil in a white crystalline solid (phosphine oxide). The white solid was triturated with EtOAc and purified by chromatography on an LPS-1 silica column. The fractions obtained were (A) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-(2-oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, (B) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-(2-methoxy)ethendiyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, and (C) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-(2,2-dimethoxy)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester.
	With acetic acid; In toluene;	A. [1beta,2alpha(5Z),3alpha,4beta]-7-[3-(2-Oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester Into a dry 1000 ml round bottom 3-necked flask containing a stir bar was added dried 12.9 g (37.7 mmoles) methoxymethyltriphenylphosphonium chloride ((C6 H5)3 P+ --CH2 OCH3 Cl-) and 235 ml distilled toluene (stored over molecular sieves). The resulting suspension was stirred in an ice-bath, under argon, until cold and then a 1.55M solution of 18.3 ml (28.3 mmol) of potassium t-amylate in toluene was added dropwise. A bright red solution formed which was stirred at 0 C. for an additional 35 minutes. Thereafter, a solution of 4.97 g (18.8 mmol) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-formyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester in 60 ml toluene was added by means of a dropping funnel over a 35 minute period with the ice-bath still in place. The reaction was then quenched by addition of 2.3 g (39 mmol) acetic acid in 5 ml ether. The reaction mixture immediately turned pale yellow and was immediately poured into 200 ml saturated NH4 Cl, and extracted with ether (4*200 ml). The combined ether phases were washed with NaCl, saturated solution, and dried (MgSO4) and concentrated to yield a yellow oil in a white crystalline solid (phosphine oxide). The white solid was triturated with EtOAc and purified by chromatography on an LPS-1 silica column. The fractions obtained were (A) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-(2-oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, (B) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-(2-methoxy)ethendiyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester and (C) 1beta,2alpha(5Z),3alpha,4beta]-7-[3-(2,2-dimethoxy)ethyl-7-oxabicyclo[2.2.1]-hept-2-yl]-5-heptenoic acid methyl ester.
	With acetic acid; In toluene;	A. [1beta,2alpha(5Z),3alpha,4beta]-7-[3-(2-Oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester Into a dry 100 ml round bottom 3-necked flask containing a stir bar was added dried 12.9 g (37.7 mmoles) methoxymethyltriphenylphosphonium chloride ((C6 H5)3 P+ --CH2 OCH3 Cl-) and 235 ml distilled toluene (stored over molecular sieves). The resulting suspension was stirred in an ice-bath, under argon, until cold and then a 1.55M solution of 18.3 ml (28.3 mmol) of potassium t-amylate in toluene was added dropwise. A bright red solution formed which was stirred at 0 C. for an additional 35 minutes. Thereafter, a solution of 4.97 g (18.8 mmol) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-formyl-7-oxabicyclo[2.2.1]-hept-2-yl]-5-heptenoic acid, methyl ester in 60 ml toluene was added by means of a dropping funnel over a 35 minute period with the ice-bath still in place. The reaction was then quenched by addition of 2.3 g (39 mmol) acetic acid in 5 ml ether. The reaction mixture immediately turned pale yellow and was immediately poured into 200 ml saturated NH4 Cl, and extracted with ether (4*200 ml). The combined ether phases were washed with NaCl, saturated solution, and dried (MgSO 4) and concentrated to yield a yellow oil in a white crystalline solid (phosphine oxide). The white solid was triturated with EtOAc and the mother liquor was purified by chromatography on an LPS-1 silica column. The fractions obtained were (A) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-(2-oxo)ethyl-7-oxabicycklo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, (B) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-(2-methoxy)-ethendiyl-7-oxabicyclo[2.2.1.]hept-2-yl]-5-heptenoic acid, methyl ester, and (C) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-(2,2-dimethoxy)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester.
	With acetic acid; In toluene;	A. [1beta,2alpha(5Z),3alpha,4beta]-7-[3-(2-Oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester Into a dry 100 ml round bottom 3-necked flask containing a stir bar was added dried 12.9 g (37.7 mmoles) methoxymethyltriphenylphosphonium chloride ((C6 H5)3 P+ --CH2 OCH3 Cl-) and 235 ml distilled toluene (stored over molecular sieves). The resulting suspension was stirred in an ice-bath, under argon, until cold and then a 1.55M solution of 18.3 ml (28.3 mmol) of potassium t-amylate in toluene was added dropwise. A bright red solution formed which was stirred at 0 C. for an additional 35 minutes. Thereafter, a solution of 4.97 g (18.8 mmol) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-formyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester in 60 ml toluene was added by means of a dropping funnel over a 35 minute period with the ice-bath still in place. The reaction was then quenched by addition of 2.3 g (39 mmol) acetic acid in 5 ml ether. The reaction mixture immediately turned pale yellow and was immediately poured into 200 ml saturated NH4 Cl, and extracted with ether (4*200 ml). The combined ether phases were washed with NaCl saturated solution, and dried (MgSO4) and concentrated to yield a yellow oil in a white crystalline solid (phosphine oxide). The white solid was triturated with EtOAc and the mother liquor was purified by chromatography on an LPS-1 silica column. The fractions obtained were (A) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-(2-oxo)ethyl-7-oxabicyclo[ 2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, (B) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-(2-methoxy)ethendiyl]-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, and (C) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-(2,2-dimethoxy)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester.

Reference： [1]Patent: US4607049,1986,A
[2]Patent: US4456616,1984,A
[3]Patent: US4456617,1984,A
[4]Patent: US4466979,1984,A
[5]Patent: US4525479,1985,A
[6]Patent: US4474803,1984,A
[7]Patent: US4526900,1985,A

20
[1α,2β(5Z),3β,4α]-7-[3-formyl-7-thiabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester [ No CAS ]
[ 41233-93-6 ]
[1β,2α(5Z),3α,4β]-7-[3-[(2-Oxo)ethyl]-7-thiabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With acetic acid; In toluene;	A. [1beta,2alpha(5Z),3alpha,4beta]-7-[3-[(2-Oxo)ethyl]-7-thiabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester Into a dry 100 ml round bottom 3-necked flask containing a stir bar is added dried 12.9 g (37.7 mmoles) methoxymethyltriphenylphosphonium chloride ((C6 H5)3 P+ --CH2 OCH3 Cl-) and 235 ml distilled toluene (stored over molecular sieves). The resulting suspension is stirred in an ice-bath, under argon, until cold and then a 1.55M solution of 18.3 ml (28.3 mmol) of potassium t-amylate in toluene is added dropwise. A bright red solution formed which is stirred at 0 C. for an additional 35 minutes. Thereafter, a solution of 4.97 g (18.8 mmol) [1alpha,2beta(5Z),3beta,4alpha]-7-[3-formyl-7-thiabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester in 60 ml toluene is added by means of a dropping funnel over a 35 minute period with the ice-bath still in place. The reaction is then quenched by addition of 2.3 g (39 mmol) acetic acid in 5 ml ether. The reaction mixture immediately turns pale yellow and is immediately poured into 200 ml saturated NH4 Cl, and extracted with ether (4*200 ml). The combined ether phases are washed with NaCl saturated solution, and dried (MgSO4) and concentrated to yield a yellow oil in a white crystalline solid (phosphine oxide). The white solid is triturated with EtOAc and the mother liquor is purified by chromatography on an LPS-1 silica column. The fractions obtained are (A) [1alpha,2beta(5Z),3beta,4alpha]-7-[3-(2-oxo)ethyl-7-thiabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, (B) [1alpha,2beta(5Z),3beta,4alpha]-7-[3-(2-methoxy)ethenyl]-7-thiabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, and (C) [1alpha,2beta(5Z),3beta,4alpha]-7-[3-(2,2-dimethoxy)ethyl-7-thiabicyclo[2.2.1]hept-2-yl]-5 -heptenoic acid, methyl ester.

Reference： [1]Patent: US4588741,1986,A

21
[1β,2α(5Z),3α,4β]-7-[(3-formyl)-7-thiabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester [ No CAS ]
[ 41233-93-6 ]
[1β,2α(5Z),3α,4β]-7-[3-[(2-Oxo)ethyl]-7-thiabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With acetic acid; In toluene;	A. [1beta,2alpha(5Z),3alpha,4beta]-7-[3-[(2-Oxo)ethyl]-7-thiabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester Into a dry 100 ml round bottom 3-necked flask containing a stir bar is added dried 12.9 g (37.7 mmoles) methoxymethyltriphenylphosphonium chloride ((C6 H5)3 P+ -CH2 OCH3 Cl-) and 235 ml distilled toluene (stored over molecular sieves). The resulting suspension is stirred in an ice-bath, under argon, until cold and then a 1.55M solution of 18.3 ml (28.3 mmol) of potassium t-amylate in toluene was added dropwise. A bright red solution formed which is stirred at 0 C. for an additional 35 minutes. Thereafter, a solution of 5.26 g (18.8 mmol) [1beta,2alpha(5Z),3alpha,4beta]-7-(3-formyl)-7-thiabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester in 60 ml toluene is added by means of a dropping funnel over a 35 minute period with the ice-bath still in place. The reaction is then quenched by addition of 2.3 g (39 mmol) acetic acid in 5 ml ether. The reaction mixture is immediately poured into 200 ml saturated NH4 Cl, and extracted with ether (4*200 ml). The combined ether phases are washed with NaCl saturated solution, and dried (MgSO4) and concentrated to yield a yellow oil in a white crystalline solid (phosphine oxide). The white solid is triturated with EtOAc and the mother liquor is purified by chromatography on an LPS-1 silica column. The fractions obtained are (A) [beta,2alpha(5Z), 3alpha,4beta]-7-[[3-(2-oxo)ethyl]bicyclo[2.2.1]-hept-2-yl]-5-heptenoic acid, methyl ester, (B) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-(2-methoxy)ethenyl]bicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, and (C) [1beta,2alpha(Z),3alpha,4beta]-7-[[3-(2,2-dimethoxy)-ethyl]bicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester.
	With acetic acid; In toluene;	A. [1beta,2alpha(Z),3alpha,4beta]-7-[3-(2-Oxo)ethyl-7-thiabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester Into a dry 100 ml round bottom 3-necked flask containing a stir bar is added dried 12.9 g (37.7 mmoles) methoxymethyltriphenylphosphonium chloride ((C6 H5)3 P+ --CH2 OCH3 Cl-) and 235 ml distilled toluene (stored over molecular sieves). The resulting suspension is stirred in an ice-bath, under argon, until cold and than a 1.55 M solution of 18.3 ml (28.3 mmol) of potassium t-amylate in toluene is added dropwise. A bright red solution forms which is stirred at 0 C. for an additional 35 minutes. Thereafter, a solution of (18.8 mmol) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-formyl-7-thiabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester in 60 ml toluene is added by means of a dropping funnel over a 35 minute period with the ice-bath still in place. The reaction is then quenched by addition of 2.3 g (39 mmol) acetic acid in 5 ml ether. The reaction mixture is immediately poured into 200 ml saturated NH4 Cl, and extracted with ether (4*200 ml). The combined ether phases are washed with NaCl, saturated solution, and dried (MgSO4) and concentrated to yield a solid (phosphine oxide). The white solid is triturated with EtOAc and the mother liquor is purified by chromatography on an LPS-1 silica column. The fractions obtained are (A) [1beta,2alpha(Z),3alpha,4beta]-7-[3-(2-oxo)ethyl-7-thiabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, (B) [1beta,2alpha(Z),3alpha,4beta]-7-[3-(2-methoxy)-ethenyl-7-thiabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, and (C) [1beta,2alpha(Z),3alpha,4beta]-7-[3-(2,2-dimethoxy)ethyl-7-thiabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester.

Reference： [1]Patent: US4595692,1986,A
[2]Patent: US4735962,1988,A

22
[ 41233-93-6 ]
[ 84565-01-5 ]

Yield	Reaction Conditions	Operation in experiment
1.75 g (51%)	In tetrahydrofuran; hexane; acetic acid; ethyl acetate; toluene;	(3) 7,7-Dimethyl-4-octenoic acid To a stirred solution of 13.7 g (31.9 mmol) of Part A(2) phosphonium bromide in 60 mL of dry THF under argon at -15 was added dropwise 32 mL (1.72M in toluene, 57.9 mmol, Callery Chem) of potassium t-amylate solution over 10 minutes. The mixture was stirred for 0.5 hour then to the resulting orange reaction mixture was added slowly a solution of 2.00 g (19.9 mmol) of Part A(1) aldehyde in 5 mL of THF. The reaction mixture was stirred at -15 C. for 1 hour then at room temperature for 20 hours and quenched with 12 mL of glacial acetic acid. The resulting solution was concentrated in vacuo and the residue was partitioned between ethyl acetate (100 mL) and saturated NaHCO3 (100 mL). The organic layer was separated and the aqueous layer was extracted twice with ethyl acetate (100 mL). The combined organic layers were washed sequentially with 1% aqueous HCl, water, saturated aqueous NaHCO3, water, and brine, then dried (magnesium sulfate), and concentrated in vacuo. The residue was purified by flash chromatography (Merck silica, gradient: 1% to 100% ethyl acetate in hexane, with 0.3% glacial acetic acid) to obtain 1.75 g (51%) of title compound.

Reference： [1]Patent: US5100889,1992,A

23
[1S-[1β,2α(5Z),3α,4β]]-7-[3-Formyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester [ No CAS ]
ammonium chloride [ No CAS ]
[ 41233-93-6 ]
[1S-[1β,2α(Z),3α,4β]]-7-[3-(2-oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With acetic acid; In toluene;	A. [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-Oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester Into a dry 100 ml round bottom 3-necked flask containing a stir bar was added dried 12.9 g (37.7 mmoles) methoxymethyltriphenylphosphonium chloride ((C6 H5)3 P+ --CH2 OCH3 Cl-) and 235 ml distilled toluene (stored over molecular sieves). The resulting suspension was stirred in an ice-bath, under argon, until cold and than a 1.55M solution of 18.3 ml (28.3 mmol) of potassium t-amylate in toluene was added dropwise. A bright red solution formed which was stirred at 0 C. for an additional 35 minutes. Thereafter, a solution of 4.97 g (18.8 mmol) [1S-[1beta,2alpha(5Z),3alpha,4beta]]-7-[3-formyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester in 60 ml toluene was added by means of a dropping funnel over a 35 minute period with the ice-bath still in place. The reaction was then quenched by addition of 2.3 g (39 mmol) acetic acid in 5 ml ether. The reaction mixture immediately turned pale yellow and was immediately poured into 200 ml satured NH4 Cl, and extracted with ether (4*200 ml). The combined ether phases were washed with NaCl, saturated solution, and dried (MgSO4) and concentrated to yield a yellow oil in a white crystalline solid (phosphine oxide). The white solid was triturated with EtOAc and the mother liquor was purified by chromatography on an LPS-1 silica column. The fractions obtained were (A) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, (B) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-methoxy)ethenyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, and (C) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2,2-dimethoxy)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester. LPS-1 silica column. The fractions obtained were (A) [1S-[1beta, 2alpha(Z),3alpha,4beta]]-7-[3-(2-oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, (B) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-methoxy)ethenyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, and (C) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2,2-dimethoxy)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester.
	With acetic acid; In toluene;	A. [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-Oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester Into a dry 100 ml round bottom 3-necked flask containing a stir bar was added dried 12.9 g (37.7 mmoles) methoxymethyltriphenylphosphonium chloride ((C6 H5)3 P+ --CH2 OCH3 Cl-) and 235 ml distilled toluene (stored over molecular sieves). The resulting suspension was stirred in an ice-bath, under argon, until cold and then a 1.55M solution of 18.3 ml (28.3 mmol) of potassium t-amylate in toluene was added dropwise. A bright red solution formed which was stirred at 0 C. for an additional 35 minutes. Thereafter, a solution of 4.97 g (18.8 mmol) [1S-[1beta,2alpha(5Z),3alpha,4beta]]-7-[3-formyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester in 60 ml toluene was added by means of a dropping funnel over a 35 minute period with the ice-bath still in place. The reaction was then quenched by addition of 2.3 g (39 mmol) acetic acid in 5 ml ether. The reaction mixture immediately turned pale yellow and was immediately poured into 200 ml satured NH4 Cl, and extracted with ether (4*200 ml). The combined ether phases were washed with NaCl, saturated solution, and dried (MgSO4) and concentrated to yield a yellow oil in a white crystalline solid (phosphine oxide). The white solid was triturated with EtOAc and the mother liquor was purified by chromatography on an LPS-1 silica column. The fractions obtained were (A) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, (B) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-methoxy)ethenyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, and (C) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2,2-dimethoxy)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester.
	With acetic acid; In toluene;	A. [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-Oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester Into a dry 100 ml round bottom 3-necked flash containing a stir bar was added dried 12.9 g (37.7 mmoles) methoxymethyltriphenylphosphonium chloride ((C6 H5)3 P+ --CH2 OCH3 Cl-) and 235 ml distilled toluene (stored over molecular sieves). The resulting suspension was stirred in an ice-bath, under argon, until cold and then a 1.55M solution of 18.3 ml (28.3 mmol) of potassium t-amylate in toluene was added dropwise. A bright red solution formed which was stirred at 0 C. for an additional 35 minutes. Thereafter, a solution of 4.97 g (18.8 mmol) [1S-[1beta,2alpha(5Z),3alpha,4beta]]-7-[3-formyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester in 60 ml toluene was added by means of a dropping funnel over a 35 minute period with the ice-bath still in place. The reaction was then quenched by addition of 2.3 g (39 mmol) acetic acid in 5 ml ether. The reaction mixture immediately turned pale yellow and was immediately poured into 200 ml satured NH4 Cl, and extracted with ether (4*200 ml). The combined ether phases were washed with NaCl, saturated solution, and dried (MgSO4) and concentrated to yield a yellow oil in a white crystalline solid (phosphine oxide). The white solid was triturated with EtOAc and the mother liquor was purified by chromatography on an LPS-1 silica column. The fractions obtained were (A) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, (B) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-methoxy)ethenyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, and (C) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2,2-dimethoxy)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester.

With acetic acid; In toluene;

A. [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-Oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester Into a dry 100 ml round bottom 3-necked flask containing a stir bar was added dried 12.9 g (37.7 mmoles) methoxymethyltriphenylphosphonium chloride ((C6 H5)3 P+ --CH2 OCH3 Cl-) and 235 ml distilled toluene (stored over molecular sieves). The resulting suspension was stirred in an ice-bath, under argon, until cold and than a 1.55M solution of 18.3 ml (28.3 mmol) of potassium t-amylate in toluene was added dropwise. A bright red solution formed which was stirred at 0 C. for an additional 35 minutes. Thereafter, a solution of 4.97 g (18.8 mmol) [1S-[1beta,2alpha(5Z),3alpha,4beta]]-7-[3-formyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester in 60 ml toluene was added by means of a dropping funnel over a 35 minute period with the ice-bath still in place. The reaction was then quenched by addition of 2.3 g (39 mmol) acetic acid in 5 ml ether. The reaction mixture immediately turned pale yellow and was immediately poured into 200 ml satured NH4 Cl, and extracted with ether (4*200 ml). The combined ether phases were washed with NaCl, saturated solution, and dried (MgSO4) and concentrated to yield a yellow oil in a white crystalline solid (phosphine oxide). The white solid was triturated with EtOAc and the mother liquor was purified by chromatography on an LPS-1 silica column. The fractions obtained were (A) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-oxo)ethyl-7-oxabicyclo[2.2.1]hept-2yl]-5-heptenoic acid, methyl ester, (B) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-methoxy)ethenyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, and (C) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2,2-dimethoxy)ethyl-7-oxabicyclo[2.2.]-hept-2-yl]-5-heptonic acid, methyl ester.

Reference： [1]Patent: US4632931,1986,A
[2]Patent: US4656185,1987,A
[3]Patent: US4652576,1987,A
[4]Patent: US4638012,1987,A

24
(1α,2β,3β,4α)-5-[[[(3-formyl)-7-oxabicyclo[2.2.1]hept-2-yl]methyl]thio]pentanoic acid, methyl ester [ No CAS ]
[ 41233-93-6 ]
[ 76-05-1 ]
(1α,2β,3β,4α)-5-[[[[3-(2-Oxo)ethyl]-7-oxabicyclo[2.2.1]hept-2-yl]methyl]thio]pentanoic acid, methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hydrogencarbonate; acetic acid; In tetrahydrofuran; hexane; toluene;	B. (1alpha,2beta,3beta,4alpha)-5-[[[[3-(2-Oxo)ethyl]-7-oxabicyclo[2.2.1]hept-2-yl]methyl]thio]pentanoic acid, methyl ester Into a dry 100 ml round bottom 3-necked flask containing a stir bar is added dried 3.27 g (9.54 mmoles) methoxymethyltriphenylphosphonium chloride (C6 H5)3 P+ --CH2 OCH3 Cl-) and 30 ml distilled toluene (stored over molecular sieves) under argon. The resulting suspension is stirred in an ice-bath until cold and then a 1.4M solution of 5.73 ml (8.01 mmol) of potassium t-amylate in toluene is added dropwise. A bright red solution forms which is stirred at 0 C. for an additional 35 minutes. Thereafter, a solution of 1.08 g (3.84 mmol) of (1alpha,2beta,3beta,4alpha)-5-[[[(3-formyl)-7-oxabicyclo[2.2.1]hept-2-yl]methyl]thio]pentanoic acid, methyl ester in 10 ml toluene is added by means of a dropping funnel over a 35 minute period with the ice-bath still in place. The reaction is then quenched by addition of 2.3 g (39 mmol) acetic acid in 5 ml ether. The mixture is immediately poured into 200 ml saturated NH4 Cl, and extracted with ether (4*200 ml). The combined ether phases are washed with NaCl saturated solution, dried (MgSO4 anhydrous) and concentrated to yield an oil in a white crystalline solid (phosphine oxide). The white solid is triturated with EtOAc, removed by filtration, and the mother liquor is purified by chromatography on an LPS-1 silica column to obtain the enol-ether. The enol ether is dissolved in 20 ml of THF and is then treated with 10 ml of a 20% aqueous trifluoro acetic acid solution. After 1 hour at room temperature, the trifluoroacetic acid is neutralized by addition of solid sodium bicarbonate. The mixture is then extracted with methylene chloride. The methylene chloride extract is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. Chromatography of the crude residue on a LPS-1 silica gel column and elution with 15-30% ethyl acetate in hexane gives 1.02 g of title B aldehyde.

Reference： [1]Patent: US4654366,1987,A

25
(3aβ,4α,7α,7aβ)-exo-Octahydro-4,7-methanoisobenzofuran-1-ol [ No CAS ]
[ 41233-93-6 ]
[ 75-07-0 ]
(1α,3β,3β,4α)-3-(2-Methoxyethenyl)-bicyclo[2.2.1]heptane-2-methanol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; In tetrahydrofuran; hexane; di-isopropyl ether; water; ethyl acetate; toluene;	E. (1alpha,3beta,3beta,4alpha)-3-(2-Methoxyethenyl)-bicyclo[2.2.1]heptane-2-methanol At 0 under N2, 41.96 g (0.122 mole) of methoxymethyl triphenyl phosphonium bromide (Aldrich) was suspended in 115 ml dry THF. Keeping the reaction temperature below 5, 71.3 ml of 1.44M potassium t-amylate solution in toluene was added dropwise. The mixture was stirred 1 hour at 0, giving a homogeneous, deep red solution. A solution of 7.6 g (0.0493 mole) of Part D compound in 10 ml THF was added over 5 minutes. The reaction mixture was stirred 2 hours at room temperature. After cooling to 5, 4.8 ml (3.78 g, 0.086 mole) of acetaldehyde was added. The temperature of the reaction rose to 13. Water (100 ml) was added and the reaction mixture was neutralized to pH 7 with 10% HCl. The organic and aqueous layers were separated. The aqueous layer was extracted 5 times with 75 ml Et2 O. The combined organics were dried over MgSO4, filtered, and concentrated to a yellow oil. This was stirred with 150 ml diisopropyl ether. Precipitated triphenyl phosphine oxide was filtered off and the precipitate was washed well with ether. The filtrate was concentrated to a yellow oil (20 g). This was purified on a flash column, using 20% ethyl acetate in hexane as eluant to give 5.8 g of title enol ether (0.318 mol, 64.5%).

Reference： [1]Patent: US4647585,1987,A

26
[ 1709-14-4 ]
[ 81878-71-9 ]
[ 31253-08-4 ]
[ 41233-93-6 ]
1-(1-Carboxyethyl)-3-(S)-[(1-carboxy-3-phenylpropyl)amino]-perhydroazepin-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	In N-methyl-acetamide; tert-Amyl alcohol; ethyl acetate; toluene;	EXAMPLE 5 1-(1-Carboxyethyl)-3-[(1-carboxy-3-phenylpropyl)amino]perhydroazepin-2-one Dissolve 1.5 g 3,3-dichloroperhydroazepin-2-one [W.C. Francis et al., J. Am. Chem. Soc., 80, 6238 (1958)] in 5 ml dimethylformamide and purge the solution with nitrogen. Add 6.05 ml of 1.37M potassium t-amyloxide in t-amyl alcohol and stir for 5 minutes. Add 2.25 g ethyl 2-iodopropionate then stir the mixture for 4 days at room temperature. Concentrate the reaction in vacuo, add toluene and concentrate again. Add a second portion of toluene, filter and concentrate the filtrate in vacuo. Chromatograph the residue on silica gel with hexane:ethyl acetate (7:3). Collect those fractions containing product and isolate 786 mg of 3,3-dichloro-1-(1-ethoxycarbonylethyl)perhydroazepin-2-one. tlc: silica, hexane:ethyl acetate (7:3) Rf=0.5 NMR (CDCl3, TMS) delta1.1-2.3 (m+t+d, 10H); delta2.5-2.8 (m, 2H); delta3.4-3.7 (m, 2H); delta4.2 (q, 2H): delta5.05 (q, 1H).
	In N-methyl-acetamide; tert-Amyl alcohol; ethyl acetate; toluene;	EXAMPLE 5 1-(1-Carboxyethyl)-3-[(1-carboxy-3-phenylpropyl)amino]perhydroazepin-2-one Dissolve 1.5 g 3,3-dichloroperhydroazepin-2-one [W. C. Francis et al., J. Am. Chem. Soc., 80, 6238 (1958)] in 5 ml dimethylformamide and purge the solution with nitrogen. Add 6.05 ml of 1.37M potassium t-amyloxide in t-amyl alcohol and stir for 5 minutes. Add 2.25 g ethyl 2-iodopropionate then stir the mixture for 4 days at room temperature. Concentrate the reaction in vacuo, add toluene and concentrate again. Add a second portion of toluene, filter and concentrate the filtrate in vacuo. Chromatograph the residue on silica gel with hexane:ethyl acetate (7:3). Collect those fractions containing product and isolate 786 mg of 3,3-dichloro-1-(1-ethoxycarbonylethyl)perhydroazepin-2-one. tlc: silica, hexane:ethyl acetate (7:3) Rf=0.5 NMR (CDCl3, TMS) delta 1.1-2.3 (m+t+d, 10H); delta 2.5-2.8 (m, 2H); delta 3.4-3.7 (m, 2H); delta 4.2 (q, 2H): delta 5.05 (q, 1H).

Reference： [1]Patent: US4629787,1986,A
[2]Patent: US4680392,1987,A

27
[ 41233-93-6 ]
[ 71884-49-6 ]
[3AR-[1-(1R,2S,5R),3aα,4α,7α,7aα]]-Octahydro-1-[[5-methyl-2-(1-methylethyl)cyclohexyl]oxy]-4,7-epoxyisobenzofuran [ No CAS ]
[1α,2β(5Z),3β,4α]-7-[[3-(2-oxo)ethyl]-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With acetic acid; In toluene;	A. [1alpha,2beta(5Z),3beta,4alpha]-7-[[3-(2-Oxo)ethyl]-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester Into a dry 100 ml round bottom 3-necked flask containing a stir bar is added dried methoxymethyltriphenylphosphonium chloride ((C6 H5)3 P+ -CH2 OCH3 Cl-) (12.9 g, 37.7 mmol) and 235 ml distilled toluene (stored over molecular sieves). The resulting suspension is stirred in an ice-bath, under argon, until cold and then a 1.55M solution of 18.3 ml (28.3 mmol) of potassium t-amylate in toluene was added dropwise. A bright red solution formed which is stirred at 0 C. for an additional 35 minutes. Thereafter, a solution of 4.8 g (18.8 mmol) [1beta,2alpha(5Z),3alpha,4beta]-7-(3-formyl)-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester in 60 ml toluene is added by means of a dropping funnel over a 35 minute period with the ice-bath still in place. The reaction is then quenched by addition of 2.3 g (39 mmol) of acetic acid in 5 ml ether. The reaction mixture is immediately poured into 200 ml saturated NH4 Cl, and extracted with ether (4*200 ml). The combined ether phases are washed with NaCl saturated solution, and dried (MgSO4) and concentrated to yield a yellow oil in a white crystalline solid (phosphine oxide). This is washed with EtOAc and the material in the washings is purified by chromatography on an LPS-1 silica gel column. The fractions obtained are (A) [1beta,2alpha(5Z),3alpha,4beta]-7-[[3-(2-oxo)ethyl]-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, (B) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-(2-methoxy)ethendiyl]-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, and (C) [1beta,2alpha(5Z),3alpha,4beta]-7-[[3-(2,2-dimethoxy)ethyl]-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester.

Reference： [1]Patent: US4654364,1987,A

28
[ 41233-93-6 ]
[ 71884-49-6 ]
[3AR-[1-(1R,2S,5R),3aα,4α,7α,7aα]]Octahydro-1-[[5-methyl-2-(1-methylethyl)cyclohexyl]oxy]-4,7-epoxyisobenzofuran [ No CAS ]
[1α,2β(5Z),3β,4α]-7-[[3-(2-oxo)ethyl]-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With acetic acid; In toluene;	A. [1alpha,2beta(5Z),3beta,4alpha]-7-[[3-(2-Oxo)ethyl]-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester Into a dry 100 ml round bottom 3-necked flask containing a stir bar is added dried methoxymethyltriphenylphosphonium chloride ((C6 H5)3 P+ --CH2 OCH3 Cl-) (12.9 g, 37.7 mmol) and 235 ml distilled toluene (stored over molecular sieves). The resulting suspension is stirred in an ice-bath, under argon, until cold and then a 1.55M solution of 18.3 ml (28.3 mmol) of potassium t-amylate in toluene was added dropwise. A bright red solution formed which is stirred at 0 C. for an additional 35 minutes. Thereafter, a solution of 4.8 g (18.8 mmol) of [1beta,2alpha(5Z),3alpha,4beta]-7-(3-formyl)-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester in 60 ml toluene is added by means of a dropping funnel over a 35 minute period with the ice-bath still in place. The reaction is then quenched by addition of 2.3 g (39 mmol) of acetic acid in 5 ml ether. The mixture is immediately poured into 200 ml saturated NH4 Cl, and extracted with ether (4*200 ml). The combined ether phases are washed with NaCl saturated solution, and dried (MgSO4 anhydrous) and concentrated to yield a yellow oil in a white crystalline solid (triphenylphosphine oxide). This is washed with EtOAc and the material in the washings is purified by chromatography on an LPS-1 silica gel column. The fractions obtained are (A) [1alpha,2beta(5Z), 3beta,4alpha]-7-[[3-(2-oxo)ethyl]-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, (B) [1alpha,2beta(5Z),3beta,4alpha]-7-[3-(2-methoxy)ethendiyl]-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, and (C) [1alpha,2beta(5Z),3beta,4alpha]-7-[[3-(2,2-dimethoxy)ethyl]-7-oxabicylo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester.

Reference： [1]Patent: US4673685,1987,A

29
[1S-[1β,2α(5Z),3α,4β]]-7-[3-Formyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester [ No CAS ]
[ 41233-93-6 ]
[1β,2α(5Z),3α,4β]-7-[3-(2-Oxoethyl)-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With acetic acid; In toluene;	A. [1beta,2alpha(Z),3alpha,4beta]-7-[3-(2-Oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester Into a dry 100 ml round bottom 3-necked flask containing a stir bar was added dried 12.9 g (37.7 mmoles) methoxymethyltriphenylphosphonium chloride ((C6 H5)3 P+ --CH2 OCH3 Cl-) and 235 ml distilled toluene (stored over molecular sieves). The resulting suspension was stirred in an ice-bath, under argon, until cold and then a 1.55M solution of 18.3 ml (28.3 mmol) of potassium t-amylate in toluene was added dropwise. A bright red solution formed which was stirred at 0 C. for an additional 35 minutes. Thereafter, a solution of 4.97 g (18.8 mmol) [1S-[1beta,2alpha(5Z),3alpha,4beta]-7-[3-formyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester in 60 ml toluene was added by means of a dropping funnel over a 35 minute period with the ice-bath still in place. The reaction was then quenched by addition of 2.3 g (39 mmol) acetic acid in 5 ml ether. The reaction mixture immediately turned pale yellow and was immediately poured into 200 ml saturated NH4 Cl, and extracted with ether (4*200 ml). The combined ether phases were washed with NaCl, saturated solution, and dried (MgSO4) and concentrated to yield a yellow oil in a white crystalline solid (phosphine oxide). The white solid was triturated with EtOAc and the mother liquor was purified by chromatography on an LPS-1 silica column. The fractions obtained were (A) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, (B) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-methoxy)ethenyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, and (C) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2,2-dimethoxy)ethyl-7-oxabicyclo[2.2.1]-hept-2-yl]-5-heptenoic acid, methyl ester.

Reference： [1]Patent: US4670453,1987,A

30
[1S-[1β,2α(5Z),3α,4β]]-7-[3-Formyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester [ No CAS ]
[ 41233-93-6 ]
[1S-[1β,2α(Z),3α,4β]]-7-[3-(2-oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With acetic acid; In toluene;	A. [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-Oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester Into a dry 100 ml round bottom 3-necked flask containing a stir bar was added dried 12.9 g (37.7 mmoles) methoxymethyltriphenylphosphonium chloride ((C6 H5)3 P+ -CH2 OCH3 Cl-) and 235 ml distilled toluene (stored over molecular sieves). The resulting suspension was stirred in an ice-bath, under argon, until cold and then a 1.55M solution of 18.3 ml (28.3 mmol) of potassium t-amylate in toluene was added dropwise. A bright red solution formed which was stirred at 0 C. for an additional 35 minutes. Thereafter, a solution of 4.97 g (18.8 mmol) [1S-[1beta,2alpha(5Z),3alpha,4beta]]-7-[3-formyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester in 60 ml toluene was added by means of a dropping funnel over a 35 minute period with the ice-bath still in place. The reaction was then quenched by addition of 2.3 g (39 mmol) acetic acid in 5 ml ether. The reaction mixture immediately turned pale yellow and was immediately poured into 200 ml saturated NH4 Cl, and extracted with ether (4*200 ml). The combined ether phases were washed with NaCl, saturated solution, and dried (MgSO4) and concentrated to yield a yellow oil in a white crystalline solid (phosphine oxide). The white solid was triturated with EtOAc and the mother liquor was purified by chromatography on an LPS-1 silica column. The fractions obtained were (A) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, (B) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-methoxy)ethenyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, and (C) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2,2-dimethoxy)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester.
	With acetic acid; In toluene;	A. [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-Oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester Into a dry 100 ml round bottom 3-necked flask containing a stir bar was added dried 12.9 g (37.7 mmoles) methoxymethyltriphenylphosphonium chloride ((C6 H5)3 P+ --CH2 OCH3 Cl-) and 235 ml distilled toluene (stored over molecular sieves). The resulting suspension was stirred in an ice-bath, under argon, until cold and then a 1.55 M solution of 18.3 ml (28.3 mmol) of potassium t-amylate in toluene was added dropwise. A bright red solution formed which was stirred at 0 C. for an additional 35 minutes. Thereafter, a solution of 4.97 g (18.8 mmol) [1S-[1beta,2alpha(5Z),3alpha,4beta]]-7-[3-formyl-7-oxabicyclo[2.2.1]hept-2yl]-5-heptenoic acid, methyl ester in 60 ml toluene was added by means of a dropping funnel over a 35 minute period with the ice-bath still in place. The reaction was then quenched by addition of 2.3 g (39 mmol) acetic acid in 5 ml ether. The reaction mixture immediately turned pale yellow and was immediately poured into 200 ml saturated NH4 Cl, and extracted with ether (4*200 ml). The combined ether phases were washed with NaCl, saturated solution, and dried (MgSO4) and concentrated to yield a yellow oil in a white crystalline solid (phosphine oxide). The white solid was triturated with EtOAc and the mother liquor was purified by chromatography on an LPS-1 silica column. The fractions obtained were (A) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, (B) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-methoxy)ethenyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, and (C) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2,2-dimethoxy)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]- 5-heptenoic acid, methyl ester.
	With acetic acid; In toluene;	A. [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-Oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester Into a dry 100 ml round bottom 3-necked flask containing a stir bar was added dried 12.9 g (37.7 mmoles) methoxymethyltriphenylphosphonium chloride ((C6 H5)3 P+ --CH2 OCH3 Cl-) and 235 ml distilled toluene (stored over molecular sieves). The resulting suspension was stirred in an ice-bath, under argon, until cold and than a 1.55M solution of 18.3 ml (28.3 mmol) of potassium t-amylate in toluene was added dropwise. A bright red solution formed which was stirred at 0 C. for an additional 35 minutes. Thereafter, a solution of 4.97 g (18.8 mmol) [1S-[1beta,2alpha(5Z),3alpha,4beta]]-7-[3-formyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester in 60 ml toluene was added by means of a dropping funnel over a 35 minute period with the ice-bath still in place. The reaction was then quenched by addition of 2.3 g (39 mmol) acetic acid in 5 ml ether. The reaction mixture immediately turned pale yellow and was immediately poured into 200 ml saturated NH4 Cl, and extracted with ether (4*200 ml). The combined ether phases were washed with NaCl, saturated solution, and dried (MgSO4) and concentrated to yield a yellow oil in a white crystalline solid (phosphine oxide). The white solid was triturated with EtOAc and the mother liquor was purified by chromatography on an LPS-1 silica column. The fractions obtained were (A) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, (B) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-methoxy)ethenyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, and (C) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2,2-dimethoxy)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester.

	With acetic acid; In toluene;	A. [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-Oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester Into a dry 100 ml round bottom 3-necked flask containing a stir bar was added dried 12.9 g (37.7 mmoles) methoxymethyltriphenylphosphonium chloride ((C6 H5)3 P+ --CH2 OCH3 Cl-) and 235 ml distilled toluene (stored over molecular sieves). The resulting suspension was stirred in an ice-bath, under argon, until cold and then a 1.55M solution of 18.3 ml (28.3 mmol) of potassium t-amylate in toluene was added dropwise. A bright red solution formed which was stirred at 0 C. for an additional 35 minutes. Thereafter, a solution of 4.97 g (18.8 mmol) [1S-[1beta,2alpha(5Z),3alpha,4beta]]-7-[3-formyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester in 60 ml toluene was added by means of a dropping funnel over a 35 minute period with the ice-bath still in place. The reaction was then quenched by addition of 2.3 g (39 mmol) acetic acid in 5 ml ether. The reaction mixture immediately turned pale yellow and was immediately poured into 200 ml saturated NH4 Cl, and extracted with ether (4*200 ml). The combined ether phases were washed with NaCl, saturated solution, and dried (MgSO4) and concentrated to yield a yellow oil in a white crystalline solid (phosphine oxide). The white solid was triturated with EtOAc and the mother liquor was purified by chromatography on an LPS-1 silica column. The fractions obtained were (A) [1S-[1beta,2alpha(Z), 3alpha,4beta]]-7-[3-(2-oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, (B) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-methoxy)ethenyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, and (C) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2,2-dimethoxy)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester.
	With acetic acid; In toluene;	A. [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-Oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester Into a dry 100 ml round bottom 3-necked flask containing a stir bar was added dried 12.9 g (37.7 mmoles) methoxymethyltriphenylphosphonium chloride ((C6 H5)3 P+ --CH2 OCH3 Cl-) and 235 ml distilled toluene (stored over molecular sieves). The resulting suspension was stirred in an ice-bath, under argon, until cold and then a 1.55M solution of 18.3 ml (28.3 mmol) of potassium t-amylate in toluene was added dropwise. A bright red solution formed which was stirred at 0 C. for an additional 35 minutes. Thereafter, a solution of 4.97 g (18.8 mmol) [1S-[1beta,2alpha(5Z),3alpha,4beta]]-7-[3-formyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester in 60 ml toluene was added by means of a dropping funnel over a 35 minute period with the ice-bath still in place. The reaction was then quenched by addition of 2.3 g (39 mmol) acetic acid in 5 ml ether. The reaction mixture immediately turned pale yellow and was immediately poured into 200 ml saturated NH4 Cl, and extracted with ether (4*200 ml). The combined ether phases were washed with NaCl, saturated solution, and dried (MgSO4) and concentrated to yield a yellow oil in a white crystalline solid (phosphine oxide). The white solid was triturated with EtOAc and the mother liquor was purified by chromatography on an LPS-1 silica column. The fractions obtained were (A) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, (B) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-methoxy)ethenyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, and (C) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2,2-dimethoxy)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester.
	With acetic acid; In toluene;	A. [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-Oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester Into a dry 100 ml round bottom 3-necked flask containing a stir bar was added dried 12.9 g (37.7 mmoles) methoxymethyltriphenylphosphonium chloride ((C6 H5)3 P+ --CH2 OCH3 Cl-) and 235 ml distilled toluene (stored over molecular sieves). The resulting suspension was stirred in an ice-bath, under argon, until cold and than a 1.55M solution of 18.3 ml (28.3 mmol) of potassium t-amylate in toluene was added dropwise. A bright red solution formed which was stirred at 0 C. for an additional 35 minutes. Thereafter, a solution of 4.97 g (18.8 mmol) [1S-[1beta,2alpha(5Z),3alpha,4beta]]-7-[3-formyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester in 60 ml toluene was added by means of a dropping funnel over a 35 minute period with the ice-bath still in place. The reaction was then quenched by addition of 2.3 g (39 mmol) acetic acid in 5 ml ether. The reaction mixture immediately turned pale yellow and was immediately poured into 200 ml saturated NH4 Cl, and extracted with ether (4*200 ml). The combined ether phases were washed with NaCl, saturated solution, and dried (MgSO4) and concentrated to yield a yellow oil in a white crystalline solid (phosphine oxide). The white solid was triturated with EtOAc and the mother liquor was purified by chromatography on an LPS-1 silica column. The fractions obtained were (A) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, (B) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2-methoxy)ethenyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, and (C) [1S-[1beta,2alpha(Z),3alpha,4beta]]-7-[3-(2,2-dimethoxy)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester.

Reference： [1]Patent: US4639461,1987,A
[2]Patent: US4654357,1987,A
[3]Patent: US4647573,1987,A
[4]Patent: US4654356,1987,A
[5]Patent: US4654355,1987,A
[6]Patent: US4663336,1987,A

31
[ 41233-93-6 ]
[ 156928-25-5 ]
[1β,2α(Z),3α,4β]-7-[[3-(2-Oxo)ethyl]-bicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With acetic acid; In toluene;	A. [1beta,2alpha(Z),3alpha,4beta]-7-[[3-(2-Oxo)ethyl]-bicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester Into a dry 100 ml round bottom 3-necked flask containing a stir bar is added dried 12.9 g (37.7 mmoles) methoxymethyltriphenylphosphonium chloride ((C6 H5)3 P+ --CH2 OCH3 Cl--) and 235 ml distilled toluene (stored over molecular sieves). The resulting suspension is stirred in an ice-bath, under argon, until cold and then a 1.55M solution of 18.3 ml (28.3 mmol) of potassium t-amylate in toluene was added dropwise. A bright red solution formed which is stirred at 0 C. for an additional 35 minutes. Thereafter, a solution of 4.97 g (18.8 mmol) [1beta,2alpha(Z),3alpha,4beta]-7-(3-formyl)bicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester in 60 ml toluene is added by means of a dropping funnel over a 35 minute period with the ice-bath still in place. The reaction is then quenched by addition of 2.3 g (39 mmol) acetic acid in 5 ml ether. The reaction mixture is immediately poured into 200 ml saturated NH4 Cl, and extracted with ether (4*200 ml). The combined ether phases are washed with NaCl saturated solution, and dried (MgSO4) and concentrated to yield a yellow oil in a white crystalline solid (phosphine oxide). The white solid is triturated with EtOAc and the mother liquor is purified by chromatography on an LPS-1 silica column. The fractions obtained are (A) [1beta,2alpha(Z),3alpha,4beta]-7-[[3-(2-oxo)ethyl]bicyclo[2.2.1]-hept-2-yl]-5-heptenoic acid, methyl ester, (B) [1beta,2alpha(Z),3alpha,4beta]-7-[3-(2-methoxy)ethendiyl]bicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, and (C) [1beta, 2alpha(Z),3alpha,4beta]-7-[[3-(2,2-dimethoxy)ethyl]bicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester.

Reference： [1]Patent: US4647585,1987,A

32
[ 4009-98-7 ]
[ 41233-93-6 ]
[ 76-05-1 ]
[1β,2α(5Z),3α,4β]-7-[3-(4-Oxo)butyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		The compound is treated with methoxymethyltriphenylphosphonium chloride and potassium t-amylate employing the procedure described in Example 22. The product of the latter reaction is treated with aqueous trifluoroacetic acid to give the title A compound.

Reference： [1]Patent: US4456617,1984,A

33
ammonium chloride [ No CAS ]
[ 41233-93-6 ]
[ 71884-49-6 ]
[1β,2α(5Z),3α,4β]-7-[3-(2-Oxoethyl)-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With acetic acid; In toluene;	A. [1beta,2alpha(Z),3alpha,4beta]-7-[3-(2-Oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester Into a dry 100 ml round bottom 3-necked flask containing a stir bar was added dried 12.9 g (37.7 mmoles) methoxymethyltriphenylphosphonium chloride ((C6 H5)3 P+ --CH2 OCH3 Cl-) and 235 ml distilled toluene (stored over molecular sieves). The resulting suspension was stirred in an ice-bath, under argon, until cold and than a 1.55 M solution of 18.3 ml (28.3 mmol) of potassium t-amylate in toluene was added dropwise. A bright red solution formed which was stirred at 0 C. for an additional 35 minutes. Thereafter, a solution of 4.97 g (18.8 mmol) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-formyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester in 60 ml toluene was added by means of a dropping funnel over a 35 minute period with the ice-bath still in place. The reaction was then quenched by addition of 2.3 g (39 mmol) acetic acid in 5 ml ether. The reaction mixture immediately turned pale yellow and was immediately poured into 200 ml satured NH4 Cl, and extracted with ether (4*200 ml). The combined ether phases were washed with NaCl, saturated solution, and dried (MgSO4) and concentrated to yield a yellow oil in a white crystalline solid (phosphine oxide). The white solid was triturated with EtOAc and the mother liquor was purified by chromatography on an LPS-1 silica column. The fractions obtained were (A) [1beta,2alpha(Z),3alpha,4beta]-7-[3-(2-oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, (B) [1beta,2alpha(Z),3alpha,4beta]-7-[3-(2-methoxy)ethendiyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, and (C) [1beta,2alpha(Z),3alpha,4beta]7-[3-(2,2-dimethoxy)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester.
	With acetic acid; In toluene;	A. [1beta,2alpha(Z),3alpha,4beta]-7-[3-(2-Oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester Into a dry 100 ml round bottom 3-necked flask containing a stir bar was added dried 12.9 g (37.7 mmoles) methoxymethyltriphenylphosphonium chloride ((C6 H5)3 P+ -CH2 OCH3 Cl-) and 235 ml distilled toluene (stored over molecular sieves). The resulting suspension was stirred in an ice-bath, under argon, until cold and then a 1.55M solution of 18.3 ml (28.3 mmol) of potassium t-amylate in toluene was added dropwise. A bright red solution formed which was stirred at 0 C. for an additional 35 minutes. Thereafter, a solution of 4.97 g (18.8 mmol) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-formyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester in 60 ml toluene was added by means of a dropping funnel over a 35 minute period with the ice-bath still in place. The reaction was then quenched by addition of 2.3 g (39 mmol) acetic acid in 5 ml ether. The reaction mixture immediately turned pale yellow and was immediately poured into 200 ml satured NH4 Cl, and extracted with ether (4*200 ml). The combined ether phases were washed with NaCl, saturated solution, and dried (MgSO4) and concentrated to yield a yellow oil in a white crystalline solid (phosphine oxide). The white solid was triturated with EtOAc and the mother liquor was purified by chromatography on an LPS-1 silica column. The fractions obtained were (A) [1beta,2alpha(Z),3alpha,4beta]-7-[3-(2-oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, (B) [1beta,2alpha(Z),3alpha,4beta]-7-[3-(2-methoxy)ethendiyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, and (C) [1beta,2alpha(Z),3alpha,4beta]-7-[3-(2,2-dimethoxy)ethyl-7-oxabicyclo[2.2.1]-hept-2-yl]-5-heptenoic acid, methyl ester.

Reference： [1]Patent: US4555523,1985,A
[2]Patent: US4560698,1985,A

34
[ 41233-93-6 ]
[ 96444-22-3 ]
7-[[3-(2-Oxo)ethyl]-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With acetic acid; In toluene;	A. [1alpha,2beta(Z), 3beta,4alpha]-7-[3-(2-Oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester Into a dry 100 ml round bottom 3-necked flask containing a stir bar was added dried 12.9 g (37.7 mmoles) methoxymethyltriphenylphosphonium chloride ((C6 H5)3 P+ -CH2 OCH3 Cl-) and 235 ml distilled toluene (stored over molecular sieves). The resulting suspension was stirred in an ice-bath, under argon, until cold and then a 1.55 M solution of 18.3 ml (28.3 mmol) of potassium t-amylate in toluene was added dropwise. A bright red solution formed which was stirred at 0 C. for an additional 35 minutes. Thereafter, a solution of 4.97 g (18.8 mmol) [1alpha,2beta(Z),3beta,4alpha]-7-[3-formyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester in 60 ml toluene was added by means of a dropping funnel over a 35 minute period with the ice-bath still in place. The reaction was then quenched by addition of 2.3 g (39 mmol) acetic acid in 5 ml ether. The reaction mixture immediately turned pale yellow and was immediately poured into 200 ml saturated NH4 Cl, and extracted with ether (4*200 ml). The combined ether phases were washed with NaCl saturated solution, and dried (MgSO4) and concentrated to yield a yellow oil in a white crystalline solid (phosphine oxide). The white solid was triturated with EtOAc and the mother liquor was purified by chromatography on an LPS-1 silica column. The fractions obtained were (A) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-(2-oxo)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, (B) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-(2-methoxy)ethendiyl]-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester, and (C) [1beta,2alpha(5Z),3alpha,4beta]-7-[3-(2,2-dimethoxy)ethyl-7-oxabicyclo[2.2.1]hept-2-yl]-5-heptenoic acid, methyl ester.

Reference： [1]Patent: US4542157,1985,A

35
[ 1520-31-6 ]
[ 41233-93-6 ]
dimethyl sulphoximine potassium salt [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	In 1,2-dimethoxyethane; toluene;	EXAMPLE 3 50.40 g of a 25% solution of potassium tert.pentylate in toluene are added dropwise at 25 C. while stirring during 30 minutes to a solution of 9.31 g of dimethyl sulphoximine in 375 ml of absolute 1,2-dimethoxyethane. The suspension is evaporated to dryness under reduced pressure. There is thus obtained the dimethyl sulphoximine potassium salt starting material.

Reference： [1]Patent: US4556413,1985,A

36
[ 2857-44-5 ]
[ 41233-93-6 ]
[ 5805-10-7 ]

Yield	Reaction Conditions	Operation in experiment
	In tert-Amyl alcohol;	EXAMPLE 11 17alpha-Ethinyl-5-androstene-3beta,17beta,19-triol Dry acetylene is bubbled through dry ether for 30 minutes with stirring. Potassium t-amylate in t-amyl alcohol and 3beta,19-dihydroxy-5-androsten-17-one diacetate in ether are added via dropwise addition. Stirring is continued at room temperature for approximately 5 hours while acetylene is bubbled through the reaction mixture. The reaction mixture is acidified with aqueous ammonium chloride containing a few drops of hydrochloric acid and thoroughly extracted with ether. The combined ether extracts are washed with water, dried over magnesium sulfate and evaporated under reduced pressure. The residue remaining is crystallized from an acetone-hexane solution to yield 17alpha-ethinyl-5-androstene-3beta,17beta, 19-triol.

Reference： [1]Patent: US4139617,1979,A

37
[ 2059-52-1 ]
[ 41233-93-6 ]
[ 67212-10-6 ]

Yield	Reaction Conditions	Operation in experiment
	In tert-Amyl alcohol;	EXAMPLE 10 17alpha-Ethinyl-5alpha-androstane-3beta,17beta,19-triol Dry acetylene is bubbled through dry ether for 30 minutes with stirring. Potassium t-amylate in t-amyl alcohol and 3beta,19-dihydroxy-5alpha-androstan-17-one in ether are added dropwise to this solution. Stirring is continued at room temperature for about 5 hours while acetylene is bubbled through the reaction mixture. The reaction mixture is then acidified with aqueous ammonium chloride containing a drop of hydrochloric acid and thoroughly extracted with ether. The combined ether extracts are washed with water, dried over magnesium sulfate and evaporated under reduced pressure. The residue is crystallized from an acetonehexane solution to yield 17alpha-ethinyl-5alpha-androstane-3beta,17beta,19-triol.

Reference： [1]Patent: US4071625,1978,A

38
tetraisopropoxyaluminate-chlorocopper(II) [ No CAS ]
[ 41233-93-6 ]
tetraisopropoxyaluminate-t-amyloxycopper(II) [ No CAS ]

Reference： [1]Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical and Analytical,1989,vol. 28,p. 396 - 399

39
[ 41233-93-6 ]
[ 1079-66-9 ]
[ 1202278-84-9 ]

Reference： [1]Tetrahedron,2009,vol. 65,p. 9973 - 9982

40
[ 172222-30-9 ]
[ 1436389-67-1 ]
[ 41233-93-6 ]
C₅₆H₈₆Cl₂N₃PRu [ No CAS ]

Reference： [1]Dalton Transactions,2013,vol. 42,p. 7463 - 7467

41
[ 1530-32-1 ]
[ 41233-93-6 ]
(Z)-1-bromo-2-(prop-1-enyl)naphthalene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	In tetrahydrofuran; toluene;	EXAMPLE II Synthesis of a Ligand with Formula 21 (in Accordance with Diagram I) 1-bromo-2-(prop-1-enyl)naphthalene. To the suspension of ethyl triphenyl phosphonium bromide (3.72 g, 10.0 mmol) in anhydrous THF (8 ml), a solution is added by drops of potassium tert-amylate (5.5 ml, 9.3 mmol, 1.7 M solution in toluene) using a syringe at room temperature. After 1 hour, the reaction mixture is cooled to a temperature of 0 C., a solution is added of aldehyde with formula 20 (1.68 g, 7.16 mmol), the cooling bath is removed, and mixing is carried out for 3 hours at room temperature. Then, the reaction mixture is diluted with cyclohexane (30 ml), the sediment is filtered off, and the solvent is evaporated at reduced pressure. The residue is chromatographed on silica gel (cyclohexane), obtaining a naphthalene derivative with formula 21 in the form of an oil as a mixture of isomers E:Z=1.82:1 (1.66 g, 94%). 1H NMR (200 MHz): 8.44-8.32 (m, 1H), 7.88-7.40 (m, 5H), 7.18-7.02 (m, 0.651H), 6.76 (dd, J=11.4, 1.6 Hz, 0.351H), 6.35 (dq, J=15.8, 6.6 Hz, 0.651H), 6.00 (dq, J=11.4, 7.0 Hz, 0.351H), 2.03 (dd, J=6.6, 1.6 Hz, 0.653H), 1.88-1.82 (m, 0.353H). 13C NMR (50 MHz): 135.7, 135.1, 133.5, 133.3, 132.6, 131.0, 130.6, 129.7, 128.1, 128.0, 127.9, 127.6, 127.5, 127.4, 127.3, 127.2, 126.8, 126.2, 126.1, 124.2, 123.6, 122.5, 18.9, 14.6. HR MS was calculated for C13H11Br: 246.0044. Found: 246.0054.

Reference： [1]Patent: US2014/171607,2014,A1 .Location in patent: Page/Page column

42
[ 1530-32-1 ]
[ 41233-93-6 ]
[ 1433187-63-3 ]

Yield	Reaction Conditions	Operation in experiment
	With magnesium sulfate; In tetrahydrofuran; hexane; water; toluene;	The combined organic extracts are rinsed with a saturated solution of NaCl (2*30 ml) and dried using MgSO4, and the solvent is evaporated at reduced pressure, obtaining aldehyde in the form of a yellow solid (3.99 g, 99%). The aldehyde obtained is used for the subsequent reaction without further purification. To the suspension of ethyl triphenyl phosphonium bromide (5.69 g, 15.3 mmol) in anhydrous THF (30 ml), a solution is added by drops of potassium tert-amylate (8.7 ml, 14.7 mmol, 1.7 M solution in toluene) using a syringe at room temperature. After 1 hour, the reaction mixture is cooled to a temperature of 0 C., the solution of crude aldehyde previously obtained is added (3.32 g, 11.79 mmol) in THF (10 ml), and mixing is continued for hours at room temperature. Then, water (1 ml) is added, and dilution takes place with n-hexane (30 ml). The sediment created is filtered, and the residue is chromatographed on silica gel (cyclohexane), obtaining naphthalene derivative with formula 25 in the form of a yellow oil (3.12 g, 90%).

Reference： [1]Patent: US2014/171607,2014,A1 .Location in patent: Page/Page column

43
[ 1622928-69-1 ]
[ 1779-49-3 ]
[ 41233-93-6 ]
[ 1622928-70-4 ]

Yield	Reaction Conditions	Operation in experiment
60%		To a suspension of methyltriphenylphosphonium bromide (0.425 g, 1.189 mmol) in toluene (2 mL) was added <strong>[41233-93-6]potassium 2-methylbutan-2-olate</strong> (0.725 mL, 1.249 mmol) (ref. J. Org. Chem. 1982, 47, 1845-1855). The yellow suspension was stirred at rt for 30 minutes and a solution of benzyl 1-methoxy-4-oxocyclohexanecarboxylate (0.156 g, 0.595 mmol) in toluene (2 mL) was added. The yellow suspension was heated at 50 C. for 2 h. The mixture was cooled to rt, diluted with water (20 mL), and extracted with ethyl acetate (3*20 mL). The combined organic layers were washed with brine, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by flash chromatography using a 0-20% EtOAc in hexanes gradient and a 24 g silica gel column to give the title product (0.085 g, 0.354 mmol, 60% yield). 1H NMR (500 MHz, CHLOROFORM-d) delta=4.67 (s, 2H), 3.32 (s, 3H), 2.38-2.28 (m, 2H), 2.21-2.12 (m, 2H), 2.04-1.97 (m, 2H), 1.87-1.78 (m, 4H), 1.47 (s, 6H), 0.93 (t, J=7.5 Hz, 3H).

Reference： [1]Patent: US2014/243298,2014,A1 .Location in patent: Paragraph 0287

44
[ 1622928-64-6 ]
[ 1779-49-3 ]
[ 41233-93-6 ]
benzyl 1-ethoxy-4-methylenecyclohexanecarboxylate [ No CAS ]
tert-pentyl 1-ethoxy-4-methylenecyclohexanecarboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		To a suspension of methyltriphenylphosphonium bromide (0.517 g, 1.448 mmol) in toluene (2 mL) was added <strong>[41233-93-6]potassium 2-methylbutan-2-olate</strong> (0.882 mL, 1.520 mmol) (ref. J. Org. Chem. 1982, 47, 1845-1855). The yellow suspension was stirred at rt for 30 minutes and a solution of benzyl 1-ethoxy-4-oxocyclohexanecarboxylate (0.2 g, 0.724 mmol) in toluene (2 mL) was added. The yellow suspension was heated at 50 C. for 2 h. The mixture was cooled to rt, diluted with water (20 mL), and extracted with ethyl acetate (3×20 mL). The organic layers were washed with brine, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by flash chromatography using a 0-20% ethyl acetate in hexanes gradient and a 24 g silica gel column to give 84 mg of a mixture of the two title compounds as a clear oil (0.4:0.6 ratio of benzyl ester:tert-pentyl ester). 1H NMR (benzyl ester) (500 MHz, CHLOROFORM-d) delta=7.39-7.30 (m, 5H), 5.18 (s, 2H), 4.65 (s, 2H), 3.41 (q, J=7.1 Hz, 2H), 2.39-2.30 (m, 2H), 2.18-2.12 (m, 2H), 2.08-1.96 (m, 2H), 1.88-1.77 (m, 2H), 1.20 (t, J=6.9 Hz, 3H). 1H NMR (tert-pentyl ester) (500 MHz, CHLOROFORM-d) delta=4.65 (s, 2H), 3.45 (q, J=6.9 Hz, 2H), 2.39-2.29 (m, 2H), 2.19-2.12 (m, 2H), 2.08-1.96 (m, 2H), 1.88-1.76 (m, 4H), 1.44 (s, 6H), 1.24 (t, J=7.0 Hz, 3H), 0.90 (t, J=7.5 Hz, 3H).

Reference： [1]Patent: US2014/243298,2014,A1 .Location in patent: Paragraph 0280

45
chloro(1,3-bis(2,6-di-i-propylphenyl)imidazol-2-ylidene)gold(I) [ No CAS ]
[ 41233-93-6 ]
[Au(1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene)(O^tAm)] [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
91%	In toluene; benzene; at 20℃; for 3h;Glovebox; Darkness;	In a glovebox, a vial was charged with [Au(IPr)Cl] (49.6 mg, 80 mumol, 1 equiv.), potassium tert-amylate (25 % in toluene, 39.3 muL, 280 mumol, 3.5 equiv.) and benzene (1 mL). It was stirred in darkness at room temperature for 3 h. It was then filtered through Celite using additional benzene and concentrated to yield a white solid (49.0 mg, 91 %).

Reference： [1]Polyhedron,2014,vol. 84,p. 59 - 62
[2]Organometallics,2017,vol. 36,p. 3645 - 3653

46
3-(4-chloro-2-fluorophenyl)propanenitrile [ No CAS ]
[ 41233-93-6 ]
2-(4-chloro-2-fluorobenzyl)-3-oxobutanenitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
18.5 g	In tetrahydrofuran; ethyl acetate; toluene; at 20℃; for 0.416667h;	To the solution of 3-(4-chloro-2-fluorophenyl)propanenitrile from Step A (15.0 g, 81.7mmol) in dry tetrahydrofuran (300 mL) a 1 M solution of potassium tert-amylate in toluene (138 mL, 245 mmol) was added dropwise during 15 minutes and then ethyl acetate (8.05 mL, 81.7 mmol) was added. The reaction was carried out for 10 minutes at room temperature. Reaction mixture was poured out on the solution of hydrochloric acid (600 mL, 0.5 M). To the mixture dichloromethane was added (100 mL). Phases were separatedand aqueous phase was extracted with dichloromethane (2 x 100 mL). Organic phases were combined, dried (Na2SO4), and evaporated under reduced pressure. The product was obtained as a pale yellow oil (18.5 g) and used without further purification in the next step.

Reference： [1]Patent: WO2015/118434,2015,A1 .Location in patent: Page/Page column 32; 33

47
[ 5439-08-7 ]
[ 41233-93-6 ]
ethyl 3-(3,5-dichloropyridin-2-yl)-3-oxopropanoate [ No CAS ]