|
With diethylzinc In dichloromethane at 0 - 20℃; |
9.6.A
To a solution of cyclopentene-4-ol (5.0 g, 59.5 mmol) and Et2Zn (12.4 mL, 121 mmol) in DCM (25 mL) under N2 atmosphere at 0° C. was added CH2I2 (9.76 mL, 121 mmol) over 30 min using a syringe pump. The reaction was slowly warmed to rt and stirred overnight at which time the mixture was opened to air and slowly quenched by the addition of dilute HCl (50 mL). The mixture was diluted with EtOAc (100 mL) and filtered. The organic layer was separated, washed with H2O (100 mL) and brine (100 mL). The organics were dried over MgSO4, filtered, and concentrated to an oil which was purified by silica gel chromatography (10% EtOAc in hexanes gradient to 30% EtOAc in hexanes) to give the cyclopropyl alcohol as clear oil. |
|
With diethylzinc In hexane; dichloromethane at 0 - 20℃; Inert atmosphere; |
10.1 1) Preparation of bicyclo [3.1.0] hexane-3-ol
Cyclopenten-1-ol (20 g, 237.77 mmol)Was dissolved in dichloromethane (1000 mL), cooled to 0 ° C,Diethylzinc (1 mol / L n-hexane solution, 476 mL) was added under a nitrogen atmosphere,Diiodomethane (128 g 477.91 mmol) was added dropwise,After the addition, the reaction was allowed to proceed to room temperature overnight. The reaction solution was quenched by dropwise addition of hydrochloric acid (4 mol / L, 100 mL) at 0 ° C, diluted with ethyl acetate (500 mL) and washed with water (300 mL X 3). The organic phase was dried over anhydrous sodium sulfate,Concentration in vacuo afforded the title compound (25 g crude). |
|
Stage #1: cyclopent-3-enol With diethylzinc In hexane; dichloromethane at 0 - 5℃; for 3h;
Stage #2: diiodomethane In hexane; dichloromethane at 0 - 27℃; for 17h; Inert atmosphere; |
Bicyclo[3.1 0]hexan-3-ol
To a stirred solution of cyclopent-3-enol (130 g, 1545 mmol) in DCM (1200 mL), was added Diethyl zinc (1.0 M in Hexane, 3091 mL, 3091 mmol) drop wise at 0-5 °C over a period of 3 h followed by drop wise addition of Diiodomethane (249 mL, 3091 mmol) in DCM (300 mL) over a period of lh at 0 °C. Reaction mixture was allowed to warm to 27 °C (Note: white precipitation was observed) and stirred for l6h under N2 atmosphere. Progress of the reaction was monitored by TLC (SiCh, 20% EtO Ac/pet, Rf = 0.3, UV-inactive, PMA- active). After completion, the reaction mixture was quenched with aq saturated NH4CI solution (1.5 L) and filtered through celite bed. The aqueous layer was extracted with DCM (2X 1000 mL). The combined organic layers were dried over anhydrous NaiSCL, filtered and the filtrate was concentrated under reduced pressure to afford crude bicyclo[3. l .0]hexan-3-ol (180 g, Yield: Crude) as reddish liquid. NMR (400 MHz, CHLOROFORM-d) d = 4.41 - 4.35 (m, 1H), 2.18 - 2.05 (m, 2H), 1.73 (d, J= 13.9 Hz, 2H), 1.35 - 1.25 (m, 2H), 1.21 - 1.14 (m, 1H), 0.57 - 0.43 (m, 2H). GCMS: m/z = 98.1). |
|
Stage #1: cyclopent-3-enol With diethylzinc In hexane; dichloromethane at 0 - 5℃; for 3h; Inert atmosphere;
Stage #2: diiodomethane In hexane; dichloromethane at 0 - 27℃; for 17h; |
bicyclo [3. l.0]hexan-3-ol
To a stirred solution of cyclopent-3-enol (130 g, 1545 mmol) in DCM (1200 mL) under N2 atmosphere at 0-5 °C was added dropwise a solution of diethyl zinc in hexane (1.0 M, 3091 mL, 3091 mmol) over a period of 3 h. To the solution at 0 °C was added dropwise a solution of diiodomethane (249 mL, 3091 mmol) in DCM (300 mL) over a period of lh. The reaction mixture was allowed to warm to 27 °C upon which formation of a white precipitation was observed. The mixture stirred for 16 h. Progress of the reaction was monitored by TLC (SiCh, 20% EtOAc/pet, Rf = 0.3, UV-inactive, PMA-active). The reaction mixture was quenched via the careful addition of aq. saturated NLLCl solution (1.5 L). The mixture was filtered through pad of Celite. The aqueous layer was extracted with DCM (2 x 1L). The combined organic layers were dried over anhydrous Na2SC>4, filtered and then concentrated under reduced pressure to afford crude bicyclo [3. l.0]hexan-3-ol as red liquid, 180 g. 'H NMR (400 MHz, CDCb) d = 4.41 - 4.35 (m, 1H), 2.18 - 2.05 (m, 2H), 1.73 (d, J= 13.9 Hz, 2H), 1.35 - 1.25 (m, 2H), 1.21 - 1.14 (m, 1H), 0.57 - 0.43 (m, 2H). GCMS: m/z = 98.1). bicyclo [3.1.0]hexan-3-one |
|
Stage #1: cyclopent-3-enol With diethylzinc In hexane; dichloromethane at 0 - 5℃; for 3h;
Stage #2: diiodomethane In hexane; dichloromethane at 0 - 27℃; for 17h; Inert atmosphere; |
Bicyclo[3.1.0]hexan-3-ol
To a stirred solution of cyclopent-3-enol (130 g, 1545 mmol) in DCM (1200 mL), was added Diethyl zinc (1.0 M in Hexane, 3091 mL, 3091 mmol) drop wise at 0-5 °C over a period of 3 h followed by drop wise addition of Diiodomethane (249 mL, 3091 mmol) in DCM (300 mL) over a period of 1h at 0 °C. Reaction mixture was allowed to warm to 27 °C (Note: white precipitation was observed) and stirred for 16h under N2 atmosphere. Progress of the reaction was monitored by TLC (SiO2, 20% EtOAc/pet, Rf = 0.3, UV- inactive, PMA-active). After completion, the reaction mixture was quenched with aq saturated NH4Cl solution (1.5 L) and filtered through celite bed. The aqueous layer was extracted with DCM (2X 1000 mL). The combined organic layers were dried over anhydrous Na2SO4, filtered and the filtrate was concentrated under reduced pressure to afford crude bicyclo[3.1.0]hexan-3-ol (180 g, Yield: Crude) as reddish liquid.1H NMR (400 MHz, CHLOROFORM-d) d = 4.41 - 4.35 (m, 1H), 2.18 - 2.05 (m, 2H), 1.73 (d, J = 13.9 Hz, 2H), 1.35 - 1.25 (m, 2H), 1.21 - 1.14 (m, 1H), 0.57 - 0.43 (m, 2H). GCMS: m/z = 98.1). |
|
Stage #1: cyclopent-3-enol With diethylzinc In hexane at 0 - 5℃; for 3h; Inert atmosphere;
Stage #2: diiodomethane In hexane; dichloromethane at 0 - 27℃; for 17h; |
Preparation of bicyclo[3.1.0]hexan-3-ol
To a stirred solution of cyclopent-3-enol (130 g, 1545 mmol) in DCM (1200 mL) under N2 atmosphere at 0-5 °C was added dropwise a solution of diethyl zinc in hexane (1.0 M, 3091 mL, 3091 mmol) over a period of 3 h. To the solution at 0 °C was added dropwise a solution of diiodomethane (249 mL, 3091 mmol) in DCM (300 mL) over a period of 1h. The reaction mixture was allowed to warm to 27 °C upon which formation of a white precipitation was observed. The mixture stirred for 16 h. Progress of the reaction was monitored by TLC (SiO2, 20% EtOAc/pet, Rf = 0.3, UV-inactive, PMA-active). The reaction mixture was quenched via the careful addition of aq. saturated NH4Cl solution (1.5 L). The mixture was filtered through pad of Celite. The aqueous layer was extracted with DCM (2 x 1L). The combined organic layers were dried over anhydrous Na2SO4, filtered and then concentrated under reduced pressure to afford crude bicyclo[3.1.0]hexan-3-ol as red liquid, 180 g.1H NMR (400 MHz, CDCl3) d = 4.41 -4.35 (m, 1H), 2.18 -2.05 (m, 2H), 1.73 (d, J = 13.9 Hz, 2H), 1.35 -1.25 (m, 2H), 1.21 -1.14 (m, 1H), 0.57 -0.43 (m, 2H). GCMS: m/z = 98.1). |
|
With diethylzinc In hexane; dichloromethane at 0 - 27℃; for 20h; Inert atmosphere; |
bicyclo[3.1.0]hexan-3-ol
To a stirred solution of cyclopent-3-enol (130 g, 1545 mmol) in DCM (1200 mL), was added diethyl zinc (1.0 M in Hexane, 3091 mL, 3091 mmol) drop wise at 0-5 °C over a period of 3 h followed by drop wise addition of Diiodomethane (249 mL, 3091 mmol) in DCM (300 mL) over a period of 1 h at 0 °C. Reaction mixture was allowed to warm to 27 °C (Note: white precipitation was observed) and stirred for l6h under N2 atmosphere. Progress of the reaction was monitored by TLC (SiCh, 20% EtO Ac/pet, Rf = 0.3, UV- inactive, PMA-active). After completion, the reaction mixture was quenched with aq saturated NH4CI solution (1.5 L) and filtered through celite bed. The aqueous layer was extracted with DCM (2X 1000 mL). The combined organic layers were dried over anhydrous NaiSCL, filtered and the filtrate was concentrated under reduced pressure to afford crude bicyclo[3. l .0]hexan-3-ol (180 g, Yield: Crude) as reddish liquid. NMR (400 MHz, CHLOROFORM-d) d = 4.41 - 4.35 (m, 1H), 2.18 - 2.05 (m, 2H), 1.73 (d, J = 13.9 Hz, 2H), 1.35 - 1.25 (m, 2H), 1.21 - 1.14 (m, 1H), 0.57 - 0.43 (m, 2H). GCMS: m/z = 98.1). |
|
Stage #1: cyclopent-3-enol With diethylzinc In hexane; dichloromethane at 0 - 5℃; for 3h; Inert atmosphere;
Stage #2: diiodomethane In hexane; dichloromethane at 0 - 27℃; for 17h; |
To a stirred solution of cyclopent-3-enol (130 g, 1545 mmol) in DCM (1200 mL) under N2 atmosphere at 0-5 °C was added dropwise a solution of diethyl zinc in hexane (1.0 M, 3091 mL, 3091 mmol) over a period of 3 h. To the solution at 0 °C was added dropwise a solution of diiodomethane (249 mL, 3091 mmol) in DCM (300 mL) over a period of lh. The reaction mixture was allowed to warm to 27 °C upon which formation of a white precipitation was observed. The mixture stirred for 16 h. Progress of the reaction was monitored by TLC (S1O2, 20% EtO Ac/pet, Rf = 0.3, UV-inactive, PMA-active). The reaction mixture was quenched via the careful addition of aq. saturated NEECl solution (1.5 L). The mixture was filtered through pad of Celite. The aqueous layer was extracted with DCM (2 x 1L). The combined organic layers were dried over anhydrous NaiSOr. filtered and then concentrated under reduced pressure to afford crude bicyclo[3. l.0]hexan-3-ol as red liquid, 180 g. 'H NMR (400 MHz, CDCb) d = 4.41 - 4.35 (m, 1H), 2.18 - 2.05 (m, 2H), 1.73 (d, J= 13.9 Hz, 2H), 1.35 - 1.25 (m, 2H), 1.21 - 1.14 (m, 1H), 0.57 - 0.43 (m, 2H). GCMS: m/z = 98.1). |
|
Stage #1: cyclopent-3-enol With diethylzinc In hexane; dichloromethane at 0 - 5℃; for 3h; Inert atmosphere;
Stage #2: diiodomethane In hexane; dichloromethane at 0 - 27℃; for 17h; Inert atmosphere; |
Preparation of bicydo[3.1.0]hexan-3-ol
To a stirred solution of cyclopent-3-enol (130 g, 1545 mmol) in DCM (1200 mL) under N2 atmosphere at 0-5 °C was added dropwise a solution of diethyl zinc in hexane (1.0 M, 3091 mL, 3091 mmol) over a period of 3 h. To the solution at 0 °C was added dropwise a solution of diiodomethane (249 mL, 3091 mmol) in DCM (300 mL) over a period of lh. The reaction mixture was allowed to warm to 27 °C upon which formation of a white precipitation was observed. The mixture stirred for 16 h. Progress of the reaction was monitored by TLC (SiC>2, 20% EtOAc/pet, Rf = 0.3, UV-inactive, PMA-active). The reaction mixture was quenched via the careful addition of aq. saturated NH4CI solution (1.5 L). The mixture was filtered through pad of Celite. The aqueous layer was extracted with DCM (2 x 1L). The combined organic layers were dried over anhydrous Na2SC>4, filtered and then concentrated under reduced pressure to afford crude bicyclo[3.1.0]hexan-3-ol as red liquid, 180 g. XH NMR (400 MHz, CDCb) d = 4.41 - 4.35 (m, 1H), 2.18 - 2.05 (m, 2H), 1.73 (d, J = 13.9 Hz, 2H), 1.35 - 1.25 (m, 2H), 1.21 - 1.14 (m, 1H), 0.57 - 0.43 (m, 2H). GCMS: m/z = 98.1). |
|
Stage #1: cyclopent-3-enol With diethylzinc In hexane; dichloromethane at 0 - 5℃; for 3h; Inert atmosphere;
Stage #2: diiodomethane In hexane; dichloromethane at 0 - 27℃; for 17h; Inert atmosphere; |
To a stirred solution of cyclopent-3-enol (130 g, 1545 mmol) in DCM (1200 mL) under N2 atmosphere at 0-5 °C was added dropwise a solution of diethyl zinc in hexane (1.0 M, 3091 mL, 3091 mmol) over a period of 3 h. To the solution at 0 °C was added dropwise a solution of diiodomethane (249 mL, 3091 mmol) in DCM (300 mL) over a period of lh. The reaction mixture was allowed to warm to 27 °C upon which formation of a white precipitation was observed. The mixture stirred for 16 h. Progress of the reaction was monitored by TLC (S1O2, 20% EtOAc/pet, Rf = 0.3, UV-inactive, PMA-active). The reaction mixture was quenched via the careful addition of aq. saturated NH4CI solution (1.5 L). The mixture was filtered through pad of Celite. The aqueous layer was extracted with DCM (2 x 1L). The combined organic layers were dried over anhydrous Na2SC>4, filtered and then concentrated under reduced pressure to afford crude bicyclo[3.1.0]hexan-3-ol as red liquid, 180 g . XH NMR (400 MHz, CDCb) d = 4.41 - 4.35 (m, 1H), 2.18 - 2.05 (m, 2H), 1.73 (d, J = 13.9 Hz, 2H), 1.35 - 1.25 (m, 2H), 1.21 - 1.14 (m, 1H), 0.57 - 0.43 (m, 2H). GCMS: m/z = 98.1). |
|
Stage #1: cyclopent-3-enol With diethylzinc In hexane; dichloromethane at 0 - 5℃; for 3h; Inert atmosphere;
Stage #2: diiodomethane In hexane; dichloromethane at 0 - 27℃; for 17h; |
To a stirred solution of cyclopent-3-enol (130 g, 1545 mmol) in DCM (1200 mL) under N2 atmosphere at 0-5 °C was added dropwise a solution of diethyl zinc in hexane (1.0 M, 3091 mL, 3091 mmol) over a period of 3 h. To the solution at 0 °C was added dropwise a solution of diiodomethane (249 mL, 3091 mmol) in DCM (300 mL) over a period of lh. The reaction mixture was allowed to warm to 27 °C upon which formation of a white precipitation was observed. The mixture stirred for 16 h. Progress of the reaction was monitored by TLC (SiC>2, 20% EtOAc/pet, Rf = 0.3, UV-inactive, PMA-active). The reaction mixture was quenched via the careful addition of aq. saturated NH4CI solution (1.5 L). The mixture was filtered through pad of Celite. The aqueous layer was extracted with DCM (2 x 1L). The combined organic layers were dried over anhydrous Na2SC>4, filtered and then concentrated under reduced pressure to afford crude bicyclo[3.1.0]hexan-3-ol as red liquid, 180 g. XH NMR (400 MHz, CDCb) d = 4.41 - 4.35 (m, 1H), 2.18 - 2.05 (m, 2H), 1.73 (d, J= 13.9 Hz, 2H), 1.35 - 1.25 (m, 2H), 1.21 - 1.14 (m, 1H), 0.57 - 0.43 (m, 2H). GCMS: m/z = 98.1). |
|
Stage #1: cyclopent-3-enol With diethylzinc In hexane; dichloromethane at 0 - 5℃; for 3h; Inert atmosphere;
Stage #2: diiodomethane In hexane; dichloromethane at 0 - 27℃; for 17h; Inert atmosphere; |
To a stirred solution of cyclopent-3-enol (130 g, 1545 mmol) in DCM (1200 mL) under N2 atmosphere at 0-5 °C was added dropwise a solution of diethyl zinc in hexane (1.0 M, 3091 mL, 3091 mmol) over a period of 3 h. To the solution at 0 °C was added dropwise a solution of diiodomethane (249 mL, 3091 mmol) in DCM (300 mL) over a period of lh. The reaction mixture was allowed to warm to 27 °C upon which formation of a white precipitation was observed. The mixture stirred for 16 h. Progress of the reaction was monitored by TLC (S1O2, 20% EtOAc/pet, Rf = 0.3, UV-inactive, PMA-active). The reaction mixture was quenched via the careful addition of aq. saturated NH4CI solution (1.5 L). The mixture was filtered through pad of Celite. The aqueous layer was extracted with DCM (2 x 1L). The combined organic layers were dried over anhydrous Na2SO filtered and then concentrated under reduced pressure to afford crude bicyclo[3.1.0]hexan-3-ol as red liquid, 180 g. JH NMR (400 MHz, CDCb) d = 4.41 - 4.35 (m, 1H), 2.18 - 2.05 (m, 2H), 1.73 (d, J= 13.9 Hz, 2H), 1.35 - 1.25 (m, 2H), 1.21 - 1.14 (m, 1H), 0.57 - 0.43 (m, 2H). GCMS: m/z = 98.1). |
|
With diethylzinc In hexane; dichloromethane at 0 - 27℃; for 20h; Inert atmosphere; |
Preparation of bicyclo[3.1.0]hexan-3-ol
To a stirred solution of cyclopent-3-enol (130 g, 1545 mmol) in DCM (1200 mL) under Il2 atmosphere at 0-5 °C was added dropwise a solution of diethyl zinc in hexane (1.0 M, 3091 mL, 3091 mmol) over a period of 3 h. To the solution at 0 °C was added dropwise a solution of diiodomethane (249 mL, 3091 mmol) in DCM (300 mL) over a period of lh. The reaction mixture was allowed to warm to 27 °C upon which formation of a white precipitation was observed. The mixture stirred for 16 h. Progress of the reaction was monitored by TLC (SiO2, 20% EtOAc/pet, Rf = 0.3, UV-inactive, PMA-active). The reaction mixture was quenched via the careful addition of aq. saturated NH4CI solution (1.5 L). The mixture was filtered through pad of Celite. The aqueous layer was extracted with DCM (2 x 1L). The combined organic layers were dried over anhydrous Na2SO4filtered and then concentrated under reduced pressure to afford crude bicyclo[3.1.0]hexan-3-ol as red liquid, 180 g.1H NMR (400 MHz, CDCI3) δ = 4.41 - 4.35 (m, 1H), 2.18 - 2.05 (m, 2H), 1.73 (d, J= 13.9 Hz, 2H), 1.35 - 1.25 (m, 2H), 1.21 - 1.14 (m, 1H), 0.57 - 0.43 (m, 2H). GCMS: m/z = 98.1). |
|
Stage #1: cyclopent-3-enol With diethylzinc In hexane; dichloromethane at 0 - 5℃; for 3h; Inert atmosphere;
Stage #2: diiodomethane In hexane; dichloromethane at 0 - 27℃; for 17h; Inert atmosphere; |
To a stirred solution of cyclopent-3-enol (130 g, 1545 mmol) in DCM (1200 mL) under N2 atmosphere at 0-5 °C was added dropwise a solution of diethyl zinc in hexane (1.0 M, 3091 mL, 3091 mmol) over a period of 3 h. To the solution at 0 °C was added dropwise a solution of diiodomethane (249 mL, 3091 mmol) in DCM (300 mL) over a period of 1h. The reaction mixture was allowed to warm to 27 °C upon which formation of a white precipitation was observed. The mixture stirred for 16 h. Progress of the reaction was monitored by TLC (SiO2, 20% EtOAc/pet, Rf = 0.3, UV-inactive, PMA-active). The reaction mixture was quenched via the careful addition of aq. saturated NH4Cl solution (1.5 L). The mixture was filtered through pad of Celite. The aqueous layer was extracted with DCM (2 x 1L). The combined organic layers were dried over anhydrous Na2SO4, filtered and then concentrated under reduced pressure to afford crude bicyclo[3.1.0]hexan-3-ol as red liquid, 180 g. 1H NMR (400 MHz, CDCl3) δ = 4.41 - 4.35 (m, 1H), 2.18 - 2.05 (m, 2H), 1.73 (d, J = 13.9 Hz, 2H), 1.35 - 1.25 (m, 2H), 1.21 - 1.14 (m, 1H), 0.57 - 0.43 (m, 2H). GCMS: m/z = 98.1). |
|
Stage #1: cyclopent-3-enol With diethylzinc In hexane; dichloromethane at 0 - 5℃; for 3h; Inert atmosphere;
Stage #2: diiodomethane In hexane; dichloromethane at 0℃; for 1h; Inert atmosphere; |
To a stirred solution of cyclopent-3-enol (130 g, 1545 mmol) in DCM (1200 mL) under I b atmosphere at 0-5 °C was added dropwise a solution of diethyl zinc in hexane (1.0 M, 3091 mL, 3091 mmol) over a period of 3 h. To the solution at 0 °C was added dropwise a solution of diiodomethane (249 mL, 3091 mmol) in DCM (300 mL) over a period of lh. The reaction mixture was allowed to warm to 27 °C upon which formation of a white precipitation was observed. The mixture stirred for 16 h. Progress of the reaction was monitored by TLC (S1O2, 20% EtOAc/pet, Rf = 0.3, UV-inactive, PMA-active). The reaction mixture was quenched via the careful addition of aq. saturated NH4CI solution (1.5 L). The mixture was filtered through pad of Celite. The aqueous layer was extracted with DCM (2 x 1L). The combined organic layers were dried over anhydrous Na2SC>4, filtered and then concentrated under reduced pressure to afford crude bicyclo[3.1.0]hexan-3-ol as red liquid, 180 g. XH NMR (400 MHz, CDCh) d = 4.41 - 4.35 (m, 1H), 2.18 - 2.05 (m, 2H), 1.73 (d, J= 13.9 Hz, 2H), 1.35 - 1.25 (m, 2H), 1.21 - 1.14 (m, 1H), 0.57 - 0.43 (m, 2H). GCMS: m/z = 98.1). |
|
Stage #1: cyclopent-3-enol With diethylzinc In hexane; dichloromethane at 0 - 5℃; for 3h; Inert atmosphere;
Stage #2: diiodomethane In hexane; dichloromethane at 0 - 27℃; for 17h; Inert atmosphere; |
Preparation of bicydo[3.1.0]hexan-3-ol
To a stirred solution of cyclopent-3-enol (130 g, 1545 mmol) in DCM (1200 mL) under Il2 atmosphere at 0-5 °C was added dropwise a solution of diethyl zinc in hexane (1.0 M, 3091 mL, 3091 mmol) over a period of 3 h. To the solution at 0 °C was added dropwise a solution of diiodomethane (249 mL, 3091 mmol) in DCM (300 mL) over a period of lh. The reaction mixture was allowed to warm to 27 °C upon which formation of a white precipitation was observed. The mixture stirred for 16 h. Progress of the reaction was monitored by TLC (S1O2, 20% EtOAc/pet, Rf = 0.3, UV-inactive, PMA-active). The reaction mixture was quenched via the careful addition of aq. saturated NH4CI solution (1.5 L). The mixture was filtered through pad of Celite. The aqueous layer was extracted with DCM (2 x 1L). The combined organic layers were dried over anhydrous Na2SC>4, filtered and then concentrated under reduced pressure to afford crude bicyclo[3.1.0]hexan-3-ol as red liquid, 180 g. XH NMR (400 MHz, CDCh) d = 4.41 - 4.35 (m, 1H), 2.18 - 2.05 (m, 2H), 1.73 (d, J= 13.9 Hz, 2H), 1.35 - 1.25 (m, 2H), 1.21 - 1.14 (m, 1H), 0.57 - 0.43 (m, 2H). GCMS: m/z = 98.1). |
| 180 g |
Stage #1: cyclopent-3-enol With diethylzinc In hexane; dichloromethane at 0 - 5℃; for 3h; Inert atmosphere;
Stage #2: diiodomethane In hexane; dichloromethane at 0 - 27℃; for 17h; |
(0073) To a stirred solution of cyclopent-3-enol (130 g, 1545 mmol) in DCM (1200 mL) under (0074) N2 atmosphere at 0-5 °C was added dropwise a solution of diethyl zinc in hexane (1.0 M, 3091 mL, 3091 mmol) over a period of 3 h. To the solution at 0 °C was added dropwise a solution of diiodomethane (249 mL, 3091 mmol) in DCM (300 mL) over a period of lh. The reaction mixture was allowed to warm to 27 °C upon which formation of a white precipitation was observed. The mixture stirred for 16 h. Progress of the reaction was monitored by TLC (S1O2, 20% EtOAc/pet, Rf = 0.3, UV-inactive, PMA-active). The reaction mixture was quenched via the careful addition of aq. saturated NH4CI solution (1.5 L). The mixture was filtered through pad of Celite. The aqueous layer was extracted with DCM (2 x 1L). The combined organic layers were dried over anhydrous Na2SC>4, filtered and then concentrated under reduced pressure to afford crude bicyclo[3.1.0]hexan-3-ol as red liquid, 180 g. XH NMR (400 MHz, CDCb) d = 4.41 - 4.35 (m, 1H), 2.18 - 2.05 (m, 2H), 1.73 (d, J= 13.9 Hz, 2H), 1.35 - 1.25 (m, 2H), 1.21 - 1.14 (m, 1H), 0.57 - 0.43 (m, 2H). GCMS: m/z = 98.1). |
Chemistry
Pharmaceutical Intermediates
Inhibitors/Agonists
Material Science
HazMat Fee +
For Research Only
110K+ Compounds
Competitive Price
1-2 Day Shipping
