2,3-dihydro-1-(methoxycarbonyl)methyl-5-((tert-butyldimethylsiloxy)methyl)benzindene | 141943-09-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 2,3-dihydro-1-(methoxycarbonyl)methyl-5-((tert-butyldimethylsiloxy)methyl)benzindene
• 英文别名: methyl 2-[4-[[tert-butyl(dimethyl)silyl]oxymethyl]-2,3-dihydro-1H-cyclopenta[a]naphthalen-1-yl]acetate
• CAS: 141943-09-1
• 化学式: C₂₃H₃₂O₃Si
• 分子量: 384.591
• InChiKey: FSOLLRFJOCRPCJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.95
• 重原子数：
  27
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  methyl 7-(2-(3-(tert-butyldimethylsiloxy)propynyl)phenyl)-1-hept-2-en-6-ynoate 在 1,4-环己二烯 作用下， 以 氯苯 为溶剂， 以70%的产率得到2,3-dihydro-1-(methoxycarbonyl)methyl-5-((tert-butyldimethylsiloxy)methyl)benzindene
  参考文献：
  名称：

  Kinetic and mechanistic studies of the tandem enediyne-radical cyclization

  摘要：

  Enediynes 11 possessing a tethered olefin radical acceptor can participate in a tandem enediyne-radical cyclization to yield dihydrobenzindene derivatives 16. In the present study, the mechanism of this reaction was investigated utilizing kinetic studies to determine whether the mechanism was a radical chain, stepwise, or concerted process. Substrate concentration, 1,4-cyclohexadiene concentration, olefin geometry, and olefin electronics were varied. These experiments demonstrate that the reaction occurs under first-order kinetics over a wide variation in either substrate or 1,4-CHD concentration. The reaction rate is also independent of olefin geometry and olefin electronics. The rate constants for the reactions were similar and ranged from 3.0 X 10(4) s-1 to 6.0 X 10(-4) s-1. The data suggests that the tandem enediyne-radical cyclization proceeds through a distinct 1,4-diyl reactive intermediate such as 5 formed in the rate-determining enediyne cyclization step, followed by a radical cyclization to give 16. The tandem enediyne-radical cyclization mechanism is supported by trapping the intermediate biradical 18 in a tandem enediyne-6-exo-radical cyclization of 17 to give products 19a,b.

  DOI：

  10.1021/jo00072a026

文献信息

• The tandem bergman-radical cyclization: a new method for ring annulation
  作者：Janet Wisniewski Grissom、Trevor L. Calkins

  DOI：10.1016/s0040-4039(00)74199-2

  日期：1992.4

  Heading of enediynes 1a, 1b and 2 at 210° C in a sealed tube in the presence of a hydrogen atom source yields naphthalene derivatives 3a, 3b and 4 in yields of 53-72%.

  在氢原子源的存在下，在密封管中于210℃下对苯二炔1a，1b和2的抽头，得到萘衍生物3a，3b和4，产率为53-72％。
• Synthetic studies of the tandem enediyne-mono- and bisradical cyclizations
  作者：Janet Wisniewski Grissom、Trevor L. Calkins、Miles Egan

  DOI：10.1021/ja00078a013

  日期：1993.12

  The readily synthesized enediynes 12a-j possessing a tethered olefin radical acceptor can participate in a tandem enediyne-radical cyclization to yield dibydrobenzindene derivatives 14a-j. In the present study, the scope of this reaction was expanded to include a wide variety of olefin acceptors. Substitution at both ends of olefin leads to the formation of two diastereomers 14b and 14c in a 3.5:1 ratio when R3 is Me and R2 is CO2Me. The structures of the dihydrobenzindene products 14b and 14c were confirmed by generating a radical from 25 by a tributyltin hydride reaction which undergoes radical cyclization; this radical is similar to the enediyne-generated radical, which also cyclizes. It was shown that, in 14i and 14j, a substituent at R1 slowed the reaction but still resulted in a good to excellent yield of product. A tandem enediyne-6-exo-radical cyclization of 16 was also carried out but did not work as well as its 5-exo counterpart 12a. Finally, an enediyne 33 containing two olefinic tethers was cyclized in a process to form tetracycle 34 where three rings were formed in one synthetic operation.
• Kinetic and mechanistic studies of the tandem enediyne-radical cyclization
  作者：Janet Wisniewski Grissom、Trevor L. Calkins

  DOI：10.1021/jo00072a026

  日期：1993.9

  Enediynes 11 possessing a tethered olefin radical acceptor can participate in a tandem enediyne-radical cyclization to yield dihydrobenzindene derivatives 16. In the present study, the mechanism of this reaction was investigated utilizing kinetic studies to determine whether the mechanism was a radical chain, stepwise, or concerted process. Substrate concentration, 1,4-cyclohexadiene concentration, olefin geometry, and olefin electronics were varied. These experiments demonstrate that the reaction occurs under first-order kinetics over a wide variation in either substrate or 1,4-CHD concentration. The reaction rate is also independent of olefin geometry and olefin electronics. The rate constants for the reactions were similar and ranged from 3.0 X 10(4) s-1 to 6.0 X 10(-4) s-1. The data suggests that the tandem enediyne-radical cyclization proceeds through a distinct 1,4-diyl reactive intermediate such as 5 formed in the rate-determining enediyne cyclization step, followed by a radical cyclization to give 16. The tandem enediyne-radical cyclization mechanism is supported by trapping the intermediate biradical 18 in a tandem enediyne-6-exo-radical cyclization of 17 to give products 19a,b.