(+)-N-BOC-CPI | 112089-38-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: (+)-N-BOC-CPI
• 英文别名: (+/-)-BOC-CPI；tert-butyl (1R,12S)-3-methyl-7-oxo-5,10-diazatetracyclo[7.4.0.01,12.02,6]trideca-2(6),3,8-triene-10-carboxylate
• CAS: 112089-38-0；119904-99-3；127379-15-1
• 化学式: C₁₇H₂₀N₂O₃
• 分子量: 300.357
• InChiKey: QRZAJMUQMIQAAY-QGHHPUGFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  22
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  62.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+)-N-BOC-CPI 在 盐酸 作用下， 以 乙酸乙酯 为溶剂， 生成 (S)-1-(chloromethyl)-5-hydroxy-8-methyl-1,2,3,6-tetrahydro-benzo[1,2-b:4,3-b']dipyrrole hydrochloride
  参考文献：
  名称：

  Coupling of cyclopropapyrroloindole (CPI) derivatives. The preparation of CC-1065, ent-CC-1065, and analogs

  摘要：

  DOI：

  10.1021/ja00256a041
• 作为产物：
  描述：

  (S)-1,6-dihydro-1-(hydroxymethyl)-8-methyl-5-(phenylmethoxy)-benzo[1,2-b:4,3-b']dipyrrole-3(2H)-carboxylic acid 1,1-dimethylethyl ester 在 palladium on activated charcoal 吡啶 、 甲酸铵 、 三乙胺 、 lithium chloride 作用下， 以 甲醇 、 水 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 生成 (+)-N-BOC-CPI
  参考文献：
  名称：

  Coupling of cyclopropapyrroloindole (CPI) derivatives. The preparation of CC-1065, ent-CC-1065, and analogs

  摘要：

  DOI：

  10.1021/ja00256a041

文献信息

• Synthesis and Properties of Substituted CBI Analogs of CC-1065 and the Duocarmycins Incorporating the 7-Methoxy-1,2,9,9a-tetrahydrocyclopropa[<i>c</i>]benz[<i>e</i>]indol-4-one (MCBI) Alkylation Subunit:  Magnitude of Electronic Effects on the Functional Reactivity
  作者：Dale L. Boger、Jeffrey A. McKie、Hui Cai、Barbara Cacciari、P. G. Baraldi

  DOI：10.1021/jo952033g

  日期：1996.1.1

  radical-alkene cyclization (24 --> 25, 32 --> 33) for completion of the synthesis of the 1,2-dihydro-3H-benz[e]indole skeleton and final Ar-3' alkylation of 28 for introduction of the activated cyclopropane. Two approaches to the implementation of the key 5-exo-trig free radical cyclization are detailed with the former proceeding with closure of 24 to provide 25 in which the required product functionalization was

  在以下文献中描述了7-甲氧基-1,2,9,9a-四氢环丙烷[c]苯并[e]吲哚-4-酮（MCBI）的合成，MCBI是带有对C4羰基的C7甲氧基的取代的CBI衍生物。努力确定对试剂的化学和功能反应性的潜在电子效应的大小。通过修饰的Stobbe缩合/ Friedel-Crafts酰化反应制备MCBI烷基化亚基的核心结构，以生成适当官能化的萘前体（15和20），然后进行5-exo-trig芳基自由基-烯烃环化（24-> 25、32-> 33）完成1，2-二氢-3H-苯并[e]吲哚骨架的合成，最后28的Ar-3'烷基化，以引入活化的环丙烷。详细介绍了实现关键的5-exo-trig自由基环化的两种方法，前者以24结束，以提供25，其中在环化之前引入了所需的产品功能化，而后者则用了环化产物的Tempo捕集器官能化的未反应的烯烃底物32提供33％。后一种简洁的方法以极好的总转化率（27-30％）以12-
• Synthesis and Evaluation of CC-1065 and Duocarmycin Analogues Incorporating the Iso-CI and Iso-CBI Alkylation Subunits:  Impact of Relocation of the C-4 Carbonyl
  作者：Dale L. Boger、Robert M. Garbaccio、Qing Jin

  DOI：10.1021/jo971686p

  日期：1997.12.1

  The synthesis of 2-(tert-Butyloxycarbonyl)-1, 2, 9, 9a-tetrahydrocyclopropa[c]benzo[f]indol-8-one (31, N-BOC-iso-CBI) and 1-(tert-Butyloxycarbonyl)-4-hydroxy-3-[[(methanesulfonyl)oxy]methyl]-2, 3-dihydroindole (19, seco-N-BOC-iso-CI) containing an isomeric structural modification in the CC-1065 and duocarmycin alkylation subunits and their incorporation into analogues of the natural products are detailed. The approach was based on a directed ortho metalation of an appropriately functionalized benzene (13) or naphthalene (24) precursor to regiospecifically install iodine at the C-2 position. Conversion of these respective intermediates to the dihydroindole skeleton utilized an established 5-exo-trig aryl radical cyclization onto an unactivated alkene with subsequent TEMPO trap or the more recent 5-exo-trig aryl radical cyclization onto a vinyl chloride for direct synthesis of the immediate precursors. Closure of the activated cyclopropane to complete the iso-CBI nucleus was accomplished by a selective ortho spirocyclization. The evaluation of the iso-CBI-based agents revealed a significant stability comparable to that of CC-1065 and duocarmycin A, but that it is more reactive than duocarmycin SA (6 - 7x) or the direct comparison CBI-based agents (5x) for which X-ray structure comparisons served to establish the basis for their inherent reaction regioselectivity and reactivity. Resolution and synthesis of a full set of natural product analogues and subsequent evaluation of their DNA alkylation properties revealed that the iso-CBI analogues, even with the relocation of the C-4 carbonyl and the most substantial structural modifications to the alkylation subunit to date, reacted at comparable rates and retain the identical and characteristic sequence selectivity of CC-1065 and the duocarmycins. This observation is inconsistent with the proposal that a sequence-dependent C-4 carbonyl protonation by strategically located DNA backbone phosphates controls the DNA alkylation selectivity but is consistent with the proposal that it is determined by the AT-rich noncovalent binding selectivity of the agents and the steric accessibility of the N3 alkylation site. Confirmation that the DNA alkylation reaction is derived from adenine N3 addition to the least substituted carbon of the activated cyclopropane, and its quantitation (95%) was established by isolation and characterization of the depurination adenine N3 adduct. Consistent with past studies and despite the deep-seated structural change in the alkylation subunit, the agents were found to exhibit potent cytotoxic activity that correlates with their inherent reactivity.
• KELLY, ROBERT C.;GEBHARD, ILSE;WICNIENSKI, NANCY;ARISTOFF, PAUL A.;JOHNSO+, J. AMER. CHEM. SOC., 109,(1987) N 22, 6837-6838
  作者：KELLY, ROBERT C.、GEBHARD, ILSE、WICNIENSKI, NANCY、ARISTOFF, PAUL A.、JOHNSO+

  DOI：——

  日期：——
• Coupling of cyclopropapyrroloindole (CPI) derivatives. The preparation of CC-1065, ent-CC-1065, and analogs
  作者：Robert C. Kelly、Ilse Gebhard、Nancy Wicnienski、Paul A. Aristoff、Paul D. Johnson、David G. Martin

  DOI：10.1021/ja00256a041

  日期：1987.10