(3S,5S)-3,5-bis(t-butyldimethylsiloxy)-6-bromohept-6-enal | 141847-49-6

• 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: (3S,5S)-3,5-bis(t-butyldimethylsiloxy)-6-bromohept-6-enal
• 英文别名: (3S,5S)-6-bromo-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]hept-6-enal
• CAS: 141847-49-6
• 化学式: C₁₉H₃₉BrO₃Si₂
• 分子量: 451.592
• InChiKey: XVPMCRYMQZIHDI-SJORKVTESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.65
• 重原子数：
  25
• 可旋转键数：
  11
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.84
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3S,5S)-3,5-bis(t-butyldimethylsiloxy)-6-bromohept-6-enal 在 palladium diacetate 、 三苯基膦 18-冠醚-6 、 双(三甲基硅烷基)氨基钾 、 potassium carbonate 作用下， 以 乙腈 为溶剂， 反应 0.83h， 生成 methyl (Z,3S,5R)-[3,5-bis(tert-butyldimethylsilyl)oxy-2-methylenecyclohexylidene]acetate
  参考文献：
  名称：

  An efficient asymmetric synthesis of 1.alpha.,25-(OH)2 vitamin D3 A-ring synthon

  摘要：

  Chiral synthesis of the A-ring synthon 3 of 1alpha,25-dihydroxyvitamin D3 (1a) based on palladium-catalyzed cyclization of 8-bromo-2,8-nonadienoates is described. Reaction of (E)-4b and (Z)-4d in the presence of Pd(OAc)2, PPh3, and K2CO3 gave (E)-3b and (Z)-3d, respectively. Optically active 4d was prepared from 24 by asymmetric aldol reaction using 31, which was cyclized to 3d. With further reactions, 1alpha,25-dihydroxyvitamin D3 (1a) was obtained.

  DOI：

  10.1021/jo00061a028
• 作为产物：
  描述：

  Methyl 6-Bromo-5-hydroxy-3-oxo-6-heptenoate 在 咪唑 、 tetramethylammonium borohydride 、 二异丁基氢化铝 、 溶剂黄146 作用下， 以 N,N-二甲基甲酰胺 、 甲苯 、 乙腈 为溶剂， 反应 3.5h， 生成 (3S,5S)-3,5-bis(t-butyldimethylsiloxy)-6-bromohept-6-enal
  参考文献：
  名称：

  An efficient asymmetric synthesis of 1.alpha.,25-(OH)2 vitamin D3 A-ring synthon

  摘要：

  Chiral synthesis of the A-ring synthon 3 of 1alpha,25-dihydroxyvitamin D3 (1a) based on palladium-catalyzed cyclization of 8-bromo-2,8-nonadienoates is described. Reaction of (E)-4b and (Z)-4d in the presence of Pd(OAc)2, PPh3, and K2CO3 gave (E)-3b and (Z)-3d, respectively. Optically active 4d was prepared from 24 by asymmetric aldol reaction using 31, which was cyclized to 3d. With further reactions, 1alpha,25-dihydroxyvitamin D3 (1a) was obtained.

  DOI：

  10.1021/jo00061a028

文献信息

• An asymmetric synthesis of a 1α,25-dihydroxyvitamin D3 A-ring synthon
  作者：Chen Chen、David Crich

  DOI：10.1016/0040-4039(92)88109-i

  日期：1992.4

  An efficient asymmetric synthesis of the A-ring of 1α,25-dihydroxyvitamin D3 from α-bromoacrolein is described. The key steps of the synthesis are the Evans type syn-selective asymmetric aldol reaction of bromoacrolein with the boron enolate of 3-chloroacetyl-4(S)-isopropyl oxazolidinone and ring closure by Heck type reaction of a vinyl bromide onto an α,β-unsaturated ester in the exo-mode.

  描述了由α-溴丙烯醛有效地不对称合成1α，25-二羟基维生素D 3的A环。合成的关键步骤是溴丙烯醛与3-氯乙酰基-4（S）-异丙基恶唑烷酮的烯醇硼的Evans型顺选择性不对称羟醛反应，以及通过溴化乙烯在α，β上的Heck型反应进行闭环-exo模式下的不饱和酯。
• The cyclization route to the calcitriol A-ring: a formal synthesis of (+)-1α,25-dihydroxyvitamin D3
  作者：Chen Chen、David Crich

  DOI：10.1016/s0040-4020(01)88018-2

  日期：1993.9

  An efficient asymmetric synthesis of the A-ring of 1alpha,25-dihydroxyvitamin D3 from alpha-bromoacrolein is described. The key steps of the synthesis are the Evans type syn-selective asymmetric aldol reaction of bromoacrolein with the boron enolate of 3-chloroacetyl-4(S)-isopropyl oxazolidinone and ring closure by Heck type reaction of a vinyl bromide onto an alpha,beta-unsaturated ester in the exo-mode.
• Stereoselective synthesis of 1α-hydroxyvitamin D3 A-ring synthons by palladium-catalyzed cyclization
  作者：Kazuo Nagasawa、Yoshiro Zako、Hideki Ishihara、Isao Shimizu

  DOI：10.1016/s0040-4039(00)93501-9

  日期：1991.9

  Palladium-catalyzed cyclization of 8-bromo-2,8-nonadienoates proceeded stereoselectively to give 1-alpha-hydroxyvitamin D3 A-ring synthons in good yields.