(1Z,3S,5R)-1-(2-Chloroethylidene)-3,5-bis[[(1,1-dimethylethyl)dimethylsilyl]oxy]-2-methylenecyclohexane

Base Information

• Chemical Name: (1Z,3S,5R)-1-(2-Chloroethylidene)-3,5-bis[[(1,1-dimethylethyl)dimethylsilyl]oxy]-2-methylenecyclohexane
• CAS No.: 81506-25-4
• Molecular Formula: C₂₁H₄₁ClO₂Si₂
• Molecular Weight: 417.179
• DSSTox Substance ID: DTXSID601111872
• Mol file: 81506-25-4.mol

Synonyms:SCHEMBL2528390;SCHEMBL6937976;DTXSID601111872;(1Z,3S,5R)-1-(2-Chloroethylidene)-3,5-bis[[(1,1-dimethylethyl)dimethylsilyl]oxy]-2-methylenecyclohexane;81506-25-4

Chemical Property of (1Z,3S,5R)-1-(2-Chloroethylidene)-3,5-bis[[(1,1-dimethylethyl)dimethylsilyl]oxy]-2-methylenecyclohexane

Chemical Property:

• Hydrogen Bond Donor Count: 0
• Hydrogen Bond Acceptor Count: 2
• Rotatable Bond Count: 7
• Exact Mass: 416.2333613
• Heavy Atom Count: 26
• Complexity: 539

Purity/Quality:

Safty Information:

• Pictogram(s):  
• Hazard Codes: 

MSDS Files:

SDS file from LookChem

Useful:

• Canonical SMILES: CC(C)(C)[Si](C)(C)OC1CC(C(=C)C(=CCCl)C1)O[Si](C)(C)C(C)(C)C
• Isomeric SMILES: CC(C)(C)[Si](C)(C)O[C@H]1C[C@@H](C(=C)/C(=C\CCl)/C1)O[Si](C)(C)C(C)(C)C

Technology Process of (1Z,3S,5R)-1-(2-Chloroethylidene)-3,5-bis[[(1,1-dimethylethyl)dimethylsilyl]oxy]-2-methylenecyclohexane

There total 31 articles about (1Z,3S,5R)-1-(2-Chloroethylidene)-3,5-bis[[(1,1-dimethylethyl)dimethylsilyl]oxy]-2-methylenecyclohexane 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: 95.0%

[3S-(1Z,3α,5β)]-2-[3,5-bis[[(1,1-dimethylethyl)dimethylsilyl]oxy]-2-methylenecyclohexylidene]ethanol (81506-24-3) → <3S-(1Z,3α,5β)>-2-<3,5-bis<<(1,1-dimethylethyl)dimethylsilyl>oxy>-2-methylenecyclohexylidene>-1-chloroethane (81506-25-4)

Guidance literature:

With N-chloro-succinimide; In dichloromethane; N,N-dimethyl-formamide; at 0 ℃;

DOI:10.1021/ja00374a052

Reference yield:

<3S-(1E,3α,5β)>-<3,5-bis<<(1,1-dimethylethyl)dimethylsilyl>oxy>-2-methylenecyclohexylidene>acetic acid ethyl ester (81506-23-2) → <3S-(1Z,3α,5β)>-2-<3,5-bis<<(1,1-dimethylethyl)dimethylsilyl>oxy>-2-methylenecyclohexylidene>-1-chloroethane (81506-25-4)

Guidance literature:

Multi-step reaction with 3 steps

1: 94.5 percent / DIBALH / hexane / 0.5 h / -70 °C

2: 77.2 percent / 9-fluorenone-4-carboxylic acid / various solvent(s) / 6 h / Irradiation

3: triphosgene; Et₃N / hexane / 1.33 h / 5 - 20 °C

With bis(trichloromethyl) carbonate; 9-oxo-9H-fluorene-4-carboxylic acid; diisobutylaluminium hydride; triethylamine; In hexane;

DOI:10.1021/jo0161577

Reference yield:

(S)-carvone oxide (39903-97-4) → <3S-(1Z,3α,5β)>-2-<3,5-bis<<(1,1-dimethylethyl)dimethylsilyl>oxy>-2-methylenecyclohexylidene>-1-chloroethane (81506-25-4)

Guidance literature:

Multi-step reaction with 9 steps

1.1: O₃/air / CH₂Cl₂ / -68 - 14 °C

2.1: Et₃N; DMAP / CH₂Cl₂; methanol / 2 h / -38 - -7 °C

3.1: methanol / 37 °C

4.1: imidazole / acetonitrile / 4 h / 20 °C

5.1: 76.1 percent / LiH / tetrahydrofuran / 21.5 h

6.1: Pd₂(dba)3(CHCl₃); PPh₃; 1,3-bis(1,1,1,3,3,3-hexafluoro-2-hydroxypropyl)benzene / toluene / 16 h / 40 °C

6.2: 84 percent / imidazole / dimethylformamide / 16 h / 20 °C

7.1: 94.5 percent / DIBALH / hexane / 0.5 h / -70 °C

8.1: 77.2 percent / 9-fluorenone-4-carboxylic acid / various solvent(s) / 6 h / Irradiation

9.1: triphosgene; Et₃N / hexane / 1.33 h / 5 - 20 °C

With 1H-imidazole; dmap; tris(dibenzylideneacetone)dipalladium⁽⁰⁾ chloroform complex; air; bis(trichloromethyl) carbonate; 1,3-bis-(1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl)-benzene; 9-oxo-9H-fluorene-4-carboxylic acid; lithium hydride; diisobutylaluminium hydride; ozone; triethylamine; triphenylphosphine; In tetrahydrofuran; methanol; hexane; dichloromethane; toluene; acetonitrile; 3.1: Criegee rearrangement / 5.1: Wittig-Horner reaction;

DOI:10.1021/jo0161577

upstream raw materials:

[3S-(1Z,3α,5β)]-2-[3,5-bis[[(1,1-dimethylethyl)dimethylsilyl]oxy]-2-methylenecyclohexylidene]ethanol

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

<3S-(1E,3α,5β)>-<3,5-bis<<(1,1-dimethylethyl)dimethylsilyl>oxy>-2-methylenecyclohexylidene>acetic acid ethyl ester

tert-butyldimethylsilyl chloride

Downstream raw materials:

[(2Z)-2-[(3S,5R)-3,5-bis(tert-butyldimethylsilanyloxy)-2-methylenecyclohexylidene]ethyl]diphenylphosphine oxide

{2-[(3S,5R)-3,5-Bis-(tert-butyl-dimethyl-silanyloxy)-2-methylene-cyclohex-(Z)-ylidene]-ethyl}-diphenyl-phosphane

calcitriol

3β-tert-butyldimethylsilyl-1α-tert-butyldimethylsilyloxy-25-trimethylsilyloxy-19-norvitamin D₃

Refernces

• 1、 Daniewski, Andrzej R.,Garofalo, Lisa M.,Hutchings, Stanley D.,Kabat, Marek M.,Liu, Wen,Okabe, Masami,Radinov, Roumen,Yiannikouros, George P.. "Efficient synthesis of the A-ring phosphine oxide building block useful for 1α,25-dihydroxy vitamin D3 and analogues". . p. 1580 - 1587. Retrieved 2007/10/03.
• 2、 Kutner, A.,Zhao, H.,Fitak, H.,Wilson, S. R.. "Synthesis of Retiferol RAD1 and RAD2, the Lead Representatives of a New Class of des-CD Analogs of Cholecalciferol". . p. 22 - 32. Retrieved 2007/10/02.