(Z,3S,5R)-[5-((tert-butyldimethylsilanyl)oxy)-3-fluoro-2-methylenecyclohexylidene]acetic acid methyl ester

Base Information

• Chemical Name: (Z,3S,5R)-[5-((tert-butyldimethylsilanyl)oxy)-3-fluoro-2-methylenecyclohexylidene]acetic acid methyl ester
• CAS No.: 214212-21-2
• Molecular Formula: C₁₆H₂₇FO₃Si
• Molecular Weight: 314.472
• Mol file: 214212-21-2.mol

Synonyms:(Z,3S,5R)-[5-((tert-butyldimethylsilanyl)oxy)-3-fluoro-2-methylenecyclohexylidene]acetic acid methyl ester

Chemical Property of (Z,3S,5R)-[5-((tert-butyldimethylsilanyl)oxy)-3-fluoro-2-methylenecyclohexylidene]acetic acid methyl ester

Chemical Property:

Purity/Quality:

Safty Information:

• Pictogram(s):  
• Hazard Codes: 

MSDS Files:

Useful:

Technology Process of (Z,3S,5R)-[5-((tert-butyldimethylsilanyl)oxy)-3-fluoro-2-methylenecyclohexylidene]acetic acid methyl ester

There total 18 articles about (Z,3S,5R)-[5-((tert-butyldimethylsilanyl)oxy)-3-fluoro-2-methylenecyclohexylidene]acetic acid methyl ester which guide to synthetic route it. The literature collected by LookChem mainly comes from the sharing of users and the free literature resources found by Internet computing technology. We keep the original model of the professional version of literature to make it easier and faster for users to retrieve and use. At the same time, we analyze and calculate the most feasible synthesis route with the highest yield for your reference as below:

synthetic route:

Reference yield: 44.0%

(3'S,5'R)-[5'-((tert-butyldimethylsilanyl)oxy)-3'-fluoro-2'-methylenecyclohexyl](phenylselanyl)acetic acid methyl ester (214212-20-1) → (E,3S,5R)-[5-((tert-butyldimethylsilanyl)oxy)-3-fluoro-2-methylenecyclohexylidene]acetic acid methyl ester + (Z,3S,5R)-[5-((tert-butyldimethylsilanyl)oxy)-3-fluoro-2-methylenecyclohexylidene]acetic acid methyl ester (214212-21-2)

Guidance literature:

With sodium periodate; In tetrahydrofuran; methanol; water; at 15 - 20 ℃; ice cooling;

DOI:10.1021/jo980764l

Reference yield:

(S)-p-mentha-6,8-dien-2-one (2244-16-8,6485-40-1) → (Z,3S,5R)-[5-((tert-butyldimethylsilanyl)oxy)-3-fluoro-2-methylenecyclohexylidene]acetic acid methyl ester (214212-21-2)

Guidance literature:

Multi-step reaction with 18 steps

1: sodium dihydridobis(2-methoxyethoxy)aluminate / toluene; tetrahydrofuran / 5 h / -70 °C

2: m-CPBA / CH₂Cl₂ / 6.5 h / -40 - -30 °C

3: 82 percent / triphenylphosphine; DEAD / toluene / 3 h / with/without ice cooling

4: 99 percent / LiOH*H₂O / tetrahydrofuran; H₂O / 4 h / 0 - 5 °C

5: tetrabutylammonium dihydrogen trifluoride / 1,2-dichloro-ethane / 24 h / 90 °C

6: 99 percent / pyridine / CH₂Cl₂ / 40 h / 15 - 25 °C

7: 85 percent / K₂CO₃ / methanol / 17 h / 20 °C

8: 83 percent / NaIO₄; OsCl₃ / tetrahydrofuran; H₂O / 4 h / 35 - 44 °C

9: 94 percent / m-CPBA / CH₂Cl₂ / 144 h / 20 °C

10: 79 percent / K₂CO₃ / methanol / 2.5 h / 20 °C

11: 91 percent / imidazole / dimethylformamide / 16 h / 20 °C

12: 72 percent / 2,2,6,6-tetramethylpiperidine; n-BuLi; ethylmagnesium chloride / tetrahydrofuran; hexane / 5 h / -70 - 20 °C

13: N-ethyldiisopropylamine / CH₂Cl₂ / 3.3 h / -70 - 20 °C

14: 25.8 g / tetrabutylammonium iodide / dimethylformamide / 15 h / 50 °C

15: molecular sieves; N-ethyldiisopropylamine / CH₂Cl₂ / 15.3 h / 5 - 20 °C

16: aq. NaOH / tetrahydrofuran / 3 h / 10 - 20 °C

17: 17.2 g / 4-DMAP; DCC / CH₂Cl₂ / 15 h / 20 °C

18: 43 percent / NaIO₄ / tetrahydrofuran; methanol; H₂O / 15 - 20 °C / ice cooling

With pyridine; 2,2,6,6-tetramethyl-piperidine; 1H-imidazole; dmap; lithium hydroxide; sodium hydroxide; sodium periodate; n-butyllithium; molecular sieve; osmium (III) chloride; ethylmagnesium chloride; tetra-(n-butyl)ammonium iodide; potassium carbonate; tetra-n-butylammonium dihydrogen trifluoride; N-ethyl-N,N-diisopropylamine; 3-chloro-benzenecarboperoxoic acid; dicyclohexyl-carbodiimide; triphenylphosphine; sodium bis(2-methoxyethoxy)aluminium dihydride; diethylazodicarboxylate; In tetrahydrofuran; methanol; hexane; dichloromethane; water; 1,2-dichloro-ethane; N,N-dimethyl-formamide; toluene; 1: Reduction / 2: Epoxidation / 3: Mitsunobu reaction / 4: Hydrolysis / 5: Ring cleavage / 6: Esterification / 7: Cyclization / 8: Oxidation / 9: Baeyer-Villiger oxidation / 10: Deacetylation / 11: silylation / 12: Rearrangement / 13: Esterification / 14: Esterification / 15: silylation; Ireland-Claisen rearrangement / 16: Hydrolysis / 17: Esterification / 18: Elimination;

DOI:10.1021/jo980764l

Reference yield:

(2S,4S)-carveol (7632-16-8,22567-18-6,20307-86-2) → (Z,3S,5R)-[5-((tert-butyldimethylsilanyl)oxy)-3-fluoro-2-methylenecyclohexylidene]acetic acid methyl ester (214212-21-2)

Guidance literature:

Multi-step reaction with 17 steps

1: m-CPBA / CH₂Cl₂ / 6.5 h / -40 - -30 °C

2: 82 percent / triphenylphosphine; DEAD / toluene / 3 h / with/without ice cooling

3: 99 percent / LiOH*H₂O / tetrahydrofuran; H₂O / 4 h / 0 - 5 °C

4: tetrabutylammonium dihydrogen trifluoride / 1,2-dichloro-ethane / 24 h / 90 °C

5: 99 percent / pyridine / CH₂Cl₂ / 40 h / 15 - 25 °C

6: 85 percent / K₂CO₃ / methanol / 17 h / 20 °C

7: 83 percent / NaIO₄; OsCl₃ / tetrahydrofuran; H₂O / 4 h / 35 - 44 °C

8: 94 percent / m-CPBA / CH₂Cl₂ / 144 h / 20 °C

9: 79 percent / K₂CO₃ / methanol / 2.5 h / 20 °C

10: 91 percent / imidazole / dimethylformamide / 16 h / 20 °C

11: 72 percent / 2,2,6,6-tetramethylpiperidine; n-BuLi; ethylmagnesium chloride / tetrahydrofuran; hexane / 5 h / -70 - 20 °C

12: N-ethyldiisopropylamine / CH₂Cl₂ / 3.3 h / -70 - 20 °C

13: 25.8 g / tetrabutylammonium iodide / dimethylformamide / 15 h / 50 °C

14: molecular sieves; N-ethyldiisopropylamine / CH₂Cl₂ / 15.3 h / 5 - 20 °C

15: aq. NaOH / tetrahydrofuran / 3 h / 10 - 20 °C

16: 17.2 g / 4-DMAP; DCC / CH₂Cl₂ / 15 h / 20 °C

17: 43 percent / NaIO₄ / tetrahydrofuran; methanol; H₂O / 15 - 20 °C / ice cooling

With pyridine; 2,2,6,6-tetramethyl-piperidine; 1H-imidazole; dmap; lithium hydroxide; sodium hydroxide; sodium periodate; n-butyllithium; molecular sieve; osmium (III) chloride; ethylmagnesium chloride; tetra-(n-butyl)ammonium iodide; potassium carbonate; tetra-n-butylammonium dihydrogen trifluoride; N-ethyl-N,N-diisopropylamine; 3-chloro-benzenecarboperoxoic acid; dicyclohexyl-carbodiimide; triphenylphosphine; diethylazodicarboxylate; In tetrahydrofuran; methanol; hexane; dichloromethane; water; 1,2-dichloro-ethane; N,N-dimethyl-formamide; toluene; 1: Epoxidation / 2: Mitsunobu reaction / 3: Hydrolysis / 4: Ring cleavage / 5: Esterification / 6: Cyclization / 7: Oxidation / 8: Baeyer-Villiger oxidation / 9: Deacetylation / 10: silylation / 11: Rearrangement / 12: Esterification / 13: Esterification / 14: silylation; Ireland-Claisen rearrangement / 15: Hydrolysis / 16: Esterification / 17: Elimination;

DOI:10.1021/jo980764l

upstream raw materials:

(3'S,5'R)-[5'-((tert-butyldimethylsilanyl)oxy)-3'-fluoro-2'-methylenecyclohexyl](phenylselanyl)acetic acid methyl ester

(S)-p-mentha-6,8-dien-2-one

(2S,4S)-carveol

(1S,2S,3R,5R)-2,3-epoxy-5-isopropenyl-2-methylcyclohex-2-enol

Downstream raw materials:

<1R-(1β,3Z,5α)>-<<3-(2-Chloroethylidene)-5-fluoro-4-methylenecyclohexyl>oxy>(1,1-dimethylethyl)dimethylsilane

<3S-(1Z,3α,5β)>-<2-<3-Fluoro-5-<<(1,1-dimethylethyl)dimethylsilyl>oxy>-2-methylenecyclohexylidene>ethyl>diphenylphosphine Oxide

<3S-(1Z,3β,5α)>-<3-Fluoro-5-<<(1,1-dimethylethyl)dimethylsilyl>oxy>-2-methylenecyclohexylidene>ethanol

Refernces