4-[(1R,3aR,4S,7aR)-4-(tert-Butyl-dimethyl-silanyloxy)-7a-methyl-octahydro-inden-1-yl]-cyclohex-3-enecarboxylic acid methyl ester | 337528-64-0

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 4-[(1R,3aR,4S,7aR)-4-(tert-Butyl-dimethyl-silanyloxy)-7a-methyl-octahydro-inden-1-yl]-cyclohex-3-enecarboxylic acid methyl ester
• CAS: 337528-64-0
• 化学式: C₂₄H₄₂O₃Si
• 分子量: 406.681
• InChiKey: HOUOISXSKGBEQY-DWGSDCDESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.49
• 重原子数：
  28.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  4-[(1R,3aR,4S,7aR)-4-(tert-Butyl-dimethyl-silanyloxy)-7a-methyl-octahydro-inden-1-yl]-cyclohex-3-enecarboxylic acid methyl ester 在 Lindlar's catalyst 氢气 作用下， 以 乙酸乙酯 为溶剂， 生成 、
  参考文献：
  名称：

  Novel side chain analogs of 1α,25-dihydroxyvitamin D3: design and synthesis of the 21,24-methano derivatives

  摘要：

  The syntheses of the new 21,24-methane derivatives of 1 alpha ,25-dihydroxyvitamin D-3 [viz. 1(S),3(R)-dihydroxy-17(R)-(1',4'-cis-(4'-(1'hydroxy-1'- hydroxy-1'-methylethyl)-cyclo-hexyl))-9, 10-seco-androsta-5(Z),7(E), 10(19)-triene (MC 2108) and its(1',4'-trans)-isomer (MC 2110)] are described. The key step is the establishment, by Diels-Alder reaction on a CD-ring side chain diene intermediate prepared from vitamin D-2, of a 1,4-disubstituted cyclohexene moiety in the side chain. Hydrogenation to a 1:1 mixture of cis and trans cyclohexane derivatives and separation of the two series at a stage prior to the standard Horner-Wittig coupling with the (Hoffmann-La Roche) ring-A building block were other important steps in the syntheses of the target analogs. The relative configurations of intermediates were assigned by NMR spectroscopy. MC 2108 and MC 2110 are of interest as conformationally locked side chain derivatives to probe the receptor interactions of not only the parent vitamin D hormone but also its biologically active symmetrical 'double side chain' analog [21-(3'-hydroxy-3'methylbutyl)-9, 10-seco-cholesta-5(Z),7(E), 10(19)-triene-1 (S),3(R),25-triol (MC 2100)], 'both' side chains of which can formally be traced out in the new analogs. The preferred conformations, inferred from an analysis of C-13-NMR characteristics, notably the chemical shift of C-17 in a series of analogs, to have the tertiary alcohol (1'-hydroxy-1'-methylethyl) substituent equatorial on the cyclohexane chair, are confirmed by molecular modeling. (C) 2001 Elsevier Science Inc. All rights reserved.

  DOI：

  10.1016/s0039-128x(00)00156-2
• 作为产物：
  描述：

  [1S-(1α,3aβ,4α,7aα)]-4-[[Dimethyl(1,1-dimethyl-ethyl)silyl]oxy]-7a-Methyl-1-(2-methyl-2-oxiranyl)octahydro-1H-indene 在 三氯化铝 、 magnesium isopropyl-cyclohexylamide 、 potassium tert-butylate 、 戴斯-马丁氧化剂 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 甲苯 为溶剂， 生成 4-[(1R,3aR,4S,7aR)-4-(tert-Butyl-dimethyl-silanyloxy)-7a-methyl-octahydro-inden-1-yl]-cyclohex-3-enecarboxylic acid methyl ester
  参考文献：
  名称：

  Novel side chain analogs of 1α,25-dihydroxyvitamin D3: design and synthesis of the 21,24-methano derivatives

  摘要：

  The syntheses of the new 21,24-methane derivatives of 1 alpha ,25-dihydroxyvitamin D-3 [viz. 1(S),3(R)-dihydroxy-17(R)-(1',4'-cis-(4'-(1'hydroxy-1'- hydroxy-1'-methylethyl)-cyclo-hexyl))-9, 10-seco-androsta-5(Z),7(E), 10(19)-triene (MC 2108) and its(1',4'-trans)-isomer (MC 2110)] are described. The key step is the establishment, by Diels-Alder reaction on a CD-ring side chain diene intermediate prepared from vitamin D-2, of a 1,4-disubstituted cyclohexene moiety in the side chain. Hydrogenation to a 1:1 mixture of cis and trans cyclohexane derivatives and separation of the two series at a stage prior to the standard Horner-Wittig coupling with the (Hoffmann-La Roche) ring-A building block were other important steps in the syntheses of the target analogs. The relative configurations of intermediates were assigned by NMR spectroscopy. MC 2108 and MC 2110 are of interest as conformationally locked side chain derivatives to probe the receptor interactions of not only the parent vitamin D hormone but also its biologically active symmetrical 'double side chain' analog [21-(3'-hydroxy-3'methylbutyl)-9, 10-seco-cholesta-5(Z),7(E), 10(19)-triene-1 (S),3(R),25-triol (MC 2100)], 'both' side chains of which can formally be traced out in the new analogs. The preferred conformations, inferred from an analysis of C-13-NMR characteristics, notably the chemical shift of C-17 in a series of analogs, to have the tertiary alcohol (1'-hydroxy-1'-methylethyl) substituent equatorial on the cyclohexane chair, are confirmed by molecular modeling. (C) 2001 Elsevier Science Inc. All rights reserved.

  DOI：

  10.1016/s0039-128x(00)00156-2