1-bromo-3,3-dimethyl-4-<(tert-butyldimethylsilyl)oxy>cyclopentene | 147727-47-7

• 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: 1-bromo-3,3-dimethyl-4-<(tert-butyldimethylsilyl)oxy>cyclopentene
• 英文别名: (1S)-4-Bromo-2,2-dimethyl-3-cyclopenten-1-YL tert-butyl(dimethyl)silyl ether；[(1S)-4-bromo-2,2-dimethylcyclopent-3-en-1-yl]oxy-tert-butyl-dimethylsilane
• CAS: 147727-47-7
• 化学式: C₁₃H₂₅BrOSi
• 分子量: 305.33
• InChiKey: MQCXWXDLOAUDFM-NSHDSACASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.09
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-bromo-3,3-dimethyl-4-<(tert-butyldimethylsilyl)oxy>cyclopentene 、 在 叔丁基锂 作用下， 生成
  参考文献：
  名称：

  研究针对不寻常的心脏毒性药物 Kalmanol 的合成。高级四环 7-Oxy-5,6-dideoxy 同系物的对映选择性构建

  摘要：

  报道了与卡尔曼醇密切相关的高度功能化的 B-homo-C-nor grayanotoxin 的首次合成。通过利用该烯酮的迈克尔受体特性和随后从中衍生的 α,β-不饱和酯，首先从 (4R)-(+)-叔丁基二甲基甲硅烷氧基环戊烯酮开发了一种对映体控制的路线，即 4 → 7 → 8. 这些实验为双环 [3.3.0] 辛烷核心的更高级取代奠定了基础。事实上，很容易获得 α-羟基酯 24-27。在这些高级中间体中，乙酰基和甲氧基具有反式 1,3-关系是必不可少的。相邻的 OR 取代基应优选大于甲氧基，以确保在随后被 1（作为其锂化衍生物）捕获期间 100% 的面部选择性。

  DOI：

  10.1021/ja9533454
• 作为产物：
  描述：

  (+/-)-1-bromo-3,3-dimethylcyclopenten-4-chloroacetate 在 咪唑 、 六甲基磷酰三胺 、 sodium hydroxide 作用下， 以 四氢呋喃 为溶剂， 反应 18.0h， 生成 1-bromo-3,3-dimethyl-4-<(tert-butyldimethylsilyl)oxy>cyclopentene
  参考文献：
  名称：

  An intramolecular cyclization approach to optically active cyclopentenyl bromides

  摘要：

  The two antipodes of 1-bromo-3,3-dimethyl-4-[(tert-butyldimethylsilyl)oxy]cyclopentene, the dextrorotatory form of which (1) is regarded as a potential synthetic precursor to kalmanol, have been prepared in a state of high enantiomeric purity from propargyl alcohol. The key steps in the abbreviated synthetic pathway involve the bromination-dehydrobromination of aldehyde 12 to give 7, the conversion of alcohol 13 to the hydroxyl-substituted bromocyclopentene 18 by a novel tandem Claisen-Sakurai reaction sequence, and efficient enzymatic resolution of 18 via its chloroacetate ester. The absolute configurational assignments are based on H-1 NMR analyses of the (R)- and (S)-MTPA esters of (-)-20.

  DOI：

  10.1021/jo00062a011

文献信息

• Studies Directed to the Synthesis of the Unusual Cardiotoxic Agent Kalmanol. Enantioselective Construction of the Advanced Tetracyclic 7-Oxy-5,6-dideoxy Congener
  作者：Stephane Borrelly、Leo A. Paquette

  DOI：10.1021/ja9533454

  日期：1996.1.1

  0]octane core. In fact, ready access was gained to the α-hydroxy esters 24−27. In these advanced intermediates, it is imperative that the acetyl and carbomethoxy groups bear a trans 1,3-relationship. The neighboring OR substituent should preferably be larger than methoxy in order to guarantee 100% facial selectivity during the ensuing capture by 1 (as its lithiated derivative). This condensation leads

  报道了与卡尔曼醇密切相关的高度功能化的 B-homo-C-nor grayanotoxin 的首次合成。通过利用该烯酮的迈克尔受体特性和随后从中衍生的 α,β-不饱和酯，首先从 (4R)-(+)-叔丁基二甲基甲硅烷氧基环戊烯酮开发了一种对映体控制的路线，即 4 → 7 → 8. 这些实验为双环 [3.3.0] 辛烷核心的更高级取代奠定了基础。事实上，很容易获得 α-羟基酯 24-27。在这些高级中间体中，乙酰基和甲氧基具有反式 1,3-关系是必不可少的。相邻的 OR 取代基应优选大于甲氧基，以确保在随后被 1（作为其锂化衍生物）捕获期间 100% 的面部选择性。
• An intramolecular cyclization approach to optically active cyclopentenyl bromides
  作者：Stephane Borrelly、Leo A. Paquette

  DOI：10.1021/jo00062a011

  日期：1993.5

  The two antipodes of 1-bromo-3,3-dimethyl-4-[(tert-butyldimethylsilyl)oxy]cyclopentene, the dextrorotatory form of which (1) is regarded as a potential synthetic precursor to kalmanol, have been prepared in a state of high enantiomeric purity from propargyl alcohol. The key steps in the abbreviated synthetic pathway involve the bromination-dehydrobromination of aldehyde 12 to give 7, the conversion of alcohol 13 to the hydroxyl-substituted bromocyclopentene 18 by a novel tandem Claisen-Sakurai reaction sequence, and efficient enzymatic resolution of 18 via its chloroacetate ester. The absolute configurational assignments are based on H-1 NMR analyses of the (R)- and (S)-MTPA esters of (-)-20.