(+)-methyl 3-bromo-2,2,4-trimethylcyclohex-3-ene-5-one carboxylate | 185851-38-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+)-methyl 3-bromo-2,2,4-trimethylcyclohex-3-ene-5-one carboxylate
• CAS: 185851-38-1
• 化学式: C₁₁H₁₅BrO₃
• 分子量: 275.142
• InChiKey: NUEPNKYRXALUQW-ZETCQYMHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.44
• 重原子数：
  15.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (+)-methyl 3-bromo-2,2,4-trimethylcyclohex-3-ene-5-one carboxylate 在 sodium tetrahydroborate 、 camphor-10-sulfonic acid 、 二异丁基氢化铝 、 potassium carbonate 、 原甲酸三甲酯 作用下， 以 甲醇 、 氯苯 为溶剂， 生成 (+)-3-bromo-2,2,4-trimethyl-6-oxa-7-methoxybicyclo<3.2.1>oct-3-ene
  参考文献：
  名称：

  Concise synthesis of taxol a-ring components: Remote diastereoselective additions of alkenyl lithiums to aldehydes

  摘要：

  The acid chloride 6 provides access to 7 (R,S and S,S) which upon bromine-lithium exchange undergoes remarkably highly diastereoselective additions to aldehydes; 7 is also readily elaborated into the acetal 10. Copyright (C) 1996 Elsevier Science Ltd

  DOI：

  10.1016/s0040-4039(96)02159-4
• 作为产物：
  描述：

  (R)-3-bromo-2,2,4-trimethyl-N-nitroso-5-oxo-N-((R)-1-phenylethyl)cyclohex-3-ene-1-carboxamide 在 sodium hydroxide 、 potassium carbonate 作用下， 以 丙酮 为溶剂， 生成 (+)-methyl 3-bromo-2,2,4-trimethylcyclohex-3-ene-5-one carboxylate
  参考文献：
  名称：

  Concise synthesis of taxol a-ring components: Remote diastereoselective additions of alkenyl lithiums to aldehydes

  摘要：

  The acid chloride 6 provides access to 7 (R,S and S,S) which upon bromine-lithium exchange undergoes remarkably highly diastereoselective additions to aldehydes; 7 is also readily elaborated into the acetal 10. Copyright (C) 1996 Elsevier Science Ltd

  DOI：

  10.1016/s0040-4039(96)02159-4

文献信息

• Taxane diterpenes 5: Synthesis of the A- and C-rings: An unusual rearrangement of an N-hydroxyimino lactone
  作者：Philip Magnus、Nicholas Westwood、Mark Spyvee、Christopher Frost、Patrick Linnane、Francis Tavares、Vince Lynch

  DOI：10.1016/s0040-4020(99)00305-1

  日期：1999.5

  Ring A of taxol was synthesized from the bromodiene 5 and acryloyl chloride to give 6, which was resolved by separation of diastereomers 7. Allylic oxidation of 7 gave 8, which on deprotection, esterification and reduction gave 11. Heating 11 followed by reduction and protection gave 13. The C-ring component was made using asymmetric Birch reduction methodology combined with standard functional group

  由溴二茂烯5和丙烯酰氯合成紫杉醇环A得到6，通过分离非对映异构体7拆分。7的烯丙基氧化得到8，经脱保护，酯化和还原反应得到11。加热11，然后还原和保护得到13。C环组件是使用不对称的Birch还原方法与标准官能团操作相结合制成的，给出了28个。将13和28合并得到29，将其转换为33。热解33不会产生一氧化氮，而是离子化为氧二烯基阳离子，最终导致34。