| 96% |
With potassium-t-butoxide; hydrogen; C27H23BrMnN2O2P In ethanol at 90℃; for 20h; |
|
| 95% |
With C15H29MnNO3P2(1+)*Br(1-); potassium-t-butoxide; hydrogen In 1,4-dioxane at 110℃; for 24h; Inert atmosphere; Autoclave; |
|
| 95% |
With sodium tetrahydridoborate; [fac-PNN]RuH(PPh)3(CO); hydrogen In tetrahydrofuran at 120℃; for 4h; Inert atmosphere; Autoclave; |
|
| 94% |
With [iPrPN(H)P]2Fe(H)(CO)(BH4); hydrogen In toluene at 115℃; for 1.5h; Glovebox; Sealed tube; |
|
| 94% |
With [bis({2‐[bis(propan‐2‐yl)phosphanyl]ethyl})amine](borohydride)(carbonyl)(hydride)iron(II); hydrogen at 115℃; for 1.5h; |
|
| 92% |
With borane-ammonia complex; boron trifluoride diethyl ether complex; tris(pentafluorophenyl)borate In 1,2-dichloro-ethane at 55℃; for 24h; Inert atmosphere; Schlenk technique; Sealed tube; |
|
| 89% |
Stage #1: methyl 4-(trifluoromethyl)benzoate With 4,4,5,5-tetramethyl-1,3,2-dioxaborolane; lithium tert-butylate In tetrahydrofuran at 100℃; for 24h; Inert atmosphere;
Stage #2: With methanol; sodium hydroxide In tetrahydrofuran at 20℃; Inert atmosphere; |
3 The preparation of 4-(trifluoromethyl)benzyl alcohol, the structural formula is as follows:
Under nitrogen protection, the starting materials 4-(trifluoromethyl)benzoic acid methyl ester (1 mmol) and pinacolborane (2.5 mmol) were added, the catalyst LiOtBu (0.05mol) and the solvent tetrahydrofuran (1.0mL) were reacted at 100°C for 24h, subsequently, 2 mol/L NaOH/MeOH solution (ie, 2 mol of sodium hydroxide per liter of methanol) was added, and the mixture was stirred at room temperature overnight, and the product separation yield was 89%. |
| 89% |
With hydrogen; C28H25BrMnN2O2P; lithium tert-butylate In propyl alcohol at 100℃; for 5h; Autoclave; |
|
| 80% |
With phenylsilane; dimanganese decacarbonyl In neat (no solvent) at 100℃; for 6h; Sealed tube; |
|
| 76% |
With n-butyllithium; [(1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene)FeCl2] In hexane; toluene at 100℃; for 20h; Inert atmosphere; Schlenk technique; Glovebox; Sealed tube; |
|
| 61% |
With hydrogen; sodium methoxide In tetrahydrofuran at 100℃; for 2.5h; |
2.4
Several other esters, whose structure and names are described in Table 3, were hydro genated under the conditions described above using preformed RuCl2(L-I). Isolated yield are given in Table 4.Table 3: Structure and names of substrates usedTable 4: Hydrogenation of esters using RuCl2(L-I) EPO Sub.: Substrate as described in Table 3.Conv.: Conversion (in %, analysed by GC after silylation) of ester to alcohol after 2h30min.Reaction conditions: Substrate (20 mmol), H2 gas (50 bars), RuCl2(L-I) 0.05 mol%,NaOMe 10 mol%, THF (14 mL) at 1000C during 2h 30min. |
| 51% |
With C24H30Cl2NPRuS2; potassium-t-butoxide; hydrogen In dichloromethane; toluene at 80℃; for 5h; Autoclave; |
|
| 46% |
With hydrogen; sodium methoxide In tetrahydrofuran at 100℃; for 2.5h; |
2.9
Several others esters (see Table 3) were hydrogenated under identical conditions as reported in Table 4 with RuCl2(L-I)2. The reaction conditions were identical to those reported above for methyl benzoate.Table 3: Structure and name of substrates used EPO Table 4: Results obtained using the general conditions described above EPO Conversion: (in %, analysed by GC after silylation) of ester to alcohol after 2h 30min. Reaction conditions: Substrate (20 mmol), H2 gas (50 bars), RuCl2(L-I)2 0.05 mol%, NaOMe 10 mol%, THF (14 mL) at 1000C during 2h 30min. |
| 46% |
With hydrogen; sodium methoxide In tetrahydrofuran at 100℃; for 2.5h; |
2.9
Several others esters (see Table 3) were hydrogenated under identical conditions as reported in Table 4 with RuCl2(L-1)2. The reaction conditions were identical to those reported above for methyl benzoate. |
| 91 %Chromat. |
Stage #1: methyl 4-(trifluoromethyl)benzoate With methyldiethoxysilane; Zinc acetate In toluene at 100℃; for 24h; Inert atmosphere;
Stage #2: With methanol; potassium hydroxide chemoselective reaction; |
|
|
Stage #1: methyl 4-(trifluoromethyl)benzoate With C33H58FeN3PSi2; phenylsilane In toluene at 20℃; for 4h; Inert atmosphere; Glovebox; Green chemistry;
Stage #2: With sodium hydroxide In toluene for 1h; Green chemistry; |
|
| 63 %Chromat. |
With 1,1'-methylene-bis(3-benzyl-1H-imidazol-3-ium) diiodide; di-μ-chlorobis-[(η6-p-cymene)chlororuthenium(II)]; potassium-t-butoxide; hydrogen In 1,4-dioxane at 100℃; for 6h; |
|
| 90 %Chromat. |
With dichlorido-bis[(2-diphenylphosphino)ethyl]amine-cobalt(II); hydrogen; sodium methoxide In 1,4-dioxane at 120℃; for 6h; Autoclave; |
|
| > 90 %Chromat. |
Stage #1: methyl 4-(trifluoromethyl)benzoate With phenylsilane; [(k2-P,N)Mn(N(SiMe3)2)] In hexadeuterobenzene at 25℃; for 4h; Inert atmosphere; Glovebox; Sealed tube;
Stage #2: With sodium hydroxide In hexadeuterobenzene; lithium hydroxide monohydrate for 18h; Inert atmosphere; Glovebox; |
|
|
With C43H42NOP3Ru; hydrogen In 1,4-dioxane; methanol at 130℃; for 17h; Glovebox; Autoclave; |
|
|
Multi-step reaction with 2 steps
1: 3C7H21Si3(1-)*La(3+) / benzene / 0.5 h / 25 °C / Inert atmosphere
2: sodium hydroxide; lithium hydroxide monohydrate / Inert atmosphere |
|
|
With methanol; tris((2-(diphenylphosphino)ethyl)amino)ruthenium monocarbonyl; hydrogen In 1,4-dioxane for 17h; Glovebox; Autoclave; Heating; |
II.II.7.1 11.7 Hydrogenation of symmetric esters, or methyl esters catalyzed by Ru(L)CO activated by methanol. General procedure:
General procedure: In an argon filled glove-box, a ca. 80 ml. Premex stainless steel autocalve fitted with a PTFE in- ner chamber and a PTFE coated magnetic stirring bar was charged with Ru(L)CO (I) (6x10-3 mmol, 4.7 mg), the specified ester (0.6 mmol), degassed, anhydrous 1 ,4-dioxane (6.0 ml.) and degassed anhydrous methanol (0.05 ml_). Hexamethylbenzene (0.15 mmol, as internal stand- ard) was added and the mixture was stirred vigorously at room temperature until full dissolution. A sample (0.1 ml.) was then taken for to-analysis (GC and NMR). After closing the reaction ves- sel was removed from the glove-box. The argon atmosphere in the autoclave was replaced with H2 by twice pressurization to 30 bar, and pressure release at room temperature. The autoclave was then pressurized with H2 gas (60 bar). The solution was heated at 130 °C (heating mantel temperature) with stirring for 17 hrs. After cooling to 0 °C, the system was vented carefully and purged for 1 minute with argon. A sample of the crude mixture (0.1 ml.) was transferred to a vial and was analyzed as-is by GC on an Agilent Technologies 6890N gas chromatography system equipped with a FID detector and an Agilent Technologies DB-1 capillary column (30 m x 0.250 mm / 1.0 pm). Another sample (0.1 ml.) was diluted with CDCI3 (0.6 ml.) in an NMR tube and analyzed by 1H-NMR. Conversion was determined by comparison to the samples at to (with hex- amethylbenzene as internal standard). NMR yield was determined by the ratio of product to starting material in the crude sample after reaction. |
| 88 %Chromat. |
With HN(CH2CH2C3H3N2Mes)2Cl2; potassium-t-butoxide; hydrogen; cobalt(II) chloride In tetrahydrofuran at 100℃; for 16h; Autoclave; Glovebox; |
|
|
With lithium aluminium hydride In tetrahydrofuran at 0 - 20℃; for 1h; Inert atmosphere; |
General procedure for the synthesis of aldehyde intermediates
General procedure: To a solution of methyl phenyl acetates (1.0 eq.) in dry THF (5mL) was added LiAlH4 (2 eq.) at 0°C under N2 atmosphere, and the resulting mixture was stirred at room temperature for 1h [23]. After complete consumption of starting material, the reaction mixture was quenched with Na+/K+ tartrate solution (∼10mL), and the mixture was filtered after being stirred at room temperature overnight. The collected filtrate was dried and concentrated to afford crude alcohol intermediate, which was oxidized by PCC (2 eq.) for 2h in CH2Cl2 (5-10mL) [24,25]. The reaction mixture was filtered through short silica column to remove brown side-product. The collected filtrate was concentrated in vacuo for next step without any purification. |
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