(+)-(1R,4S,5R,8S,9R,12S)-2,3,4,6,7,8,10,11,12-nonahydro-1,5,9,13,13',14,14',15,15'-nonamethyl-1,4:5,8:9,12-trimethanotriphenylene

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: (+)-(1R,4S,5R,8S,9R,12S)-2,3,4,6,7,8,10,11,12-nonahydro-1,5,9,13,13',14,14',15,15'-nonamethyl-1,4:5,8:9,12-trimethanotriphenylene
• 英文别名: (1R,4S,5R,8S,9R,12S)-2,3,4,6,7,8,9,10,11-nonahydro-1,5,12,13,13',14,14',15,15'-nonamethyl-1,4;5,8:9,12-trimethanotriphenylene
• 化学式: C₃₀H₄₂
• 分子量: 402.663
• InChiKey: FKEPAWZSLMFISU-BDVHUIKKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.21
• 重原子数：
  30.0
• 可旋转键数：
  0.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  (+)-3-bromo-1,7,7-trimethyl-2-(trimethylstannyl)bicyclo[2.2.1]hept-2-ene 在 噻吩-2-甲酸亚铜(I) 作用下， 以 various solvent(s) 为溶剂， 反应 2.0h， 生成 (+)-(1R,4S,5R,8S,9R,12S)-2,3,4,6,7,8,10,11,12-nonahydro-1,5,9,13,13',14,14',15,15'-nonamethyl-1,4:5,8:9,12-trimethanotriphenylene 、 (+)-(1R,4S,5R,8S,9S,12R)-2,3,4,6,7,8,9,10,11-nonahydro-1,5,12,13,13',14,14',15,15'-nonamethyl-1,4:5,8:9,12-trimethanotriphenylene
  参考文献：
  名称：

  衍生自 (+)-樟脑、(+)-苯甲酚酮和 (-)-表樟脑的对映脲-溴（三甲基甲锡烷基）双环烯烃的比较环三聚反应：桥头甲基基团对合成/抗产物比率的影响

  摘要：

  研究了桥头甲基对多环烯烃环三聚反应中顺/反非对映选择性的影响。为此，制备了三种不同的对映体纯 vic-bromo(trimethylstannyl)-取代的双环烯烃并用作探针。研究了不同铜 (II) 或 -(I) 盐的影响，并且大多数二聚中间体是独立合成和表征的。环三聚机制的一些迹象是通过旨在确定二聚的相对速率的实验提供的。结果为如何实现高效的顺式环三聚反应提供了有用的指示。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

  DOI：

  10.1002/ejoc.200400120

文献信息

• The cyclotrimerisation of (+)-camphor
  作者：Fabrizio Fabris、Alessandro De Martin、Ottorino De Lucchi

  DOI：10.1016/s0040-4039(99)01889-4

  日期：1999.12

  Naturally occurring (+)-camphor was converted into 2-bromobornene and metallated at the 3-position by lithium and trimethyltin. The latter tin derivative, treated with Cu(NO3)2·3H2O in THF affords the syn and anti cyclotrimers plus a number of byproducts. The rather unexpected formation of the anti stereoisomer plus the structure of several byproducts confirm a mechanistic proposal based on a SnSn

  天然存在的（+）樟脑转化为2-溴冰片烯，并在3位被锂和三甲基锡金属化。后一种锡衍生物经THF中的Cu（NO 3）2 ·3H 2 O处理后，可获得顺式和反式环三聚体以及许多副产物。抗立体异构体的相当意外的形成以及几种副产物的结构证实了基于SnSn偶联过程的机械方案。
• Efficient Cyclotrimerization of Bicyclic <i>v</i><i>ic</i>-Bromostannylalkenes Promoted by Copper(I) Thiophen-2-carboxylate
  作者：Giuseppe Borsato、Ottorino De Lucchi、Fabrizio Fabris、Luca Groppo、Vittorio Lucchini、Alfonso Zambon

  DOI：10.1021/jo020396s

  日期：2002.11.1

  Copper(I) thiophen-2-carboxylate was successfully employed in the trimerization of [2.2.1] bicyclic vic-bromotrimethyltin olefins (in their racemic composition), bearing different functionalities, to invariably obtain almost quantitative yields of the syn and anti tris-annelated benzenes. The two isomers come in different ratios, smaller than or equal to the statistical 1:3 ratio, depending on the steric hindrance opposed by the functionalities. In the case of enantiopure (3-bromo-4,7,7-trimethylbicyclo[2.2.1]hept-2-en-2-yl)trimethylstannane, the 1:9 ratio found with Cu(NO3)(2).3H(2)O increases to 1:6.
• Heck self-condensation of polycyclic haloalkenes: the case of (1R)-2-iodobornene
  作者：Laura Zambrini、Fabrizio Fabris、Ottorino De Lucchi、Graziano Gardenal、Fabiano Visentin、Luciano Canovese

  DOI：10.1016/s0040-4020(01)00850-x

  日期：2001.10

  The unusual reactivity of a haloalkene undergoing Heck reaction behaving both as reagent and substrate (Heck donor and acceptor) is studied and discussed in detail in the case of (1R)-2-iodo-1,7,7-trimethyl-bicyclo[2.2.1]hept-2-ene (2-iodobornene). This enantiopure substrate allows for a rational description of the mechanism which takes into account the nature of the products and the substitution of one of the substituents (iodine and proton) at carbons 2 and 3 of the bornene skeleton. Under catalytic conditions the main products are the syn and anti-cyclotrimers, a head-to-tail dimer and an arene derived from the latter. The products of the stoichiometric reaction between palladium(0) tetrakis(triphenylphosphine) and 2-iodobornene are principally trans-Pd(PPh3)(2)PhI and various dimeric species. The results are rationalized in terms of a catalytic reaction which takes into account the Pd(H)-Pd(IV) oxidation state sequence. The major products in both the catalytic and stoichiometric reactions are dimeric species with formal elimination of an iodine molecule that are unprecedented in the literature for the Heck reaction. (C) 2001 Elsevier Science Ltd. All rights reserved.