(2'S,6R)-6-ethyl-1-methoxy-6-[[2'-(methoxymethyl)pyrrolidinyl]carbonyl]-4-methyl-1,4-cyclohexadiene | 186887-36-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: (2'S,6R)-6-ethyl-1-methoxy-6-[[2'-(methoxymethyl)pyrrolidinyl]carbonyl]-4-methyl-1,4-cyclohexadiene
• 英文别名: [(1R)-1-ethyl-2-methoxy-5-methylcyclohexa-2,5-dien-1-yl]-[(2S)-2-(methoxymethyl)pyrrolidin-1-yl]methanone
• CAS: 186887-36-5
• 化学式: C₁₇H₂₇NO₃
• 分子量: 293.406
• InChiKey: VVUFAKDUEMFOQN-WMLDXEAASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2'S,6R)-6-ethyl-1-methoxy-6-[[2'-(methoxymethyl)pyrrolidinyl]carbonyl]-4-methyl-1,4-cyclohexadiene 在 盐酸 、 碘 作用下， 以 四氢呋喃 、 甲醇 、 水 为溶剂， 反应 3.0h， 生成 (2R,3R,4R)-2-ethyl-3-iodo-4-methyl-1-oxocyclohexane-2,4-carbolactone
  参考文献：
  名称：

  2-烷基和2,4-二烷基-3-碘-1-氧代环己基-2,4-碳内酯的新型断裂反应

  摘要：

  2-烷基-和2,4-二烷基-3-碘-1-氧代环己基-2,4-碳内酯经历氢氧化锂和烷氧基锂诱导​​的裂解反应，从而提供丁烯内酯，γ-羟基环己烯酮和/或γ-丁内酯。通常，产物分布受两个因素控制：（1）亲核试剂的性质和（2）环己酮在C-2和C-4处取代基的空间体积。氢氧化锂诱导的断裂提供丁烯内酯和γ-羟基环己烯酮。相反，在有限的情况下，锂醇盐促进的断裂会导致主要为5取代的γ-丁内酯以及少量的丁烯内酯。由氢氧化锂诱导的裂解产物在很大程度上受环己酮环的C-2和C-4处取代基的空间体积的影响。

  DOI：

  10.1021/jo0490853
• 作为产物：
  描述：

  (S)-2-methoxy-1-[[2'-(methoxymethyl)pyrrolidinyl]carbonyl]-5-methylbenzene 、 alkaline earth salt of/the/ methylsulfuric acid 在 氨 、 氢化钾 、 叔丁醇 、 间戊二烯 作用下， 以 四氢呋喃 为溶剂， 反应 4.5h， 以100%的产率得到(2'S,6R)-6-ethyl-1-methoxy-6-[[2'-(methoxymethyl)pyrrolidinyl]carbonyl]-4-methyl-1,4-cyclohexadiene
  参考文献：
  名称：

  2-烷基和2,4-二烷基-3-碘-1-氧代环己基-2,4-碳内酯的新型断裂反应

  摘要：

  2-烷基-和2,4-二烷基-3-碘-1-氧代环己基-2,4-碳内酯经历氢氧化锂和烷氧基锂诱导​​的裂解反应，从而提供丁烯内酯，γ-羟基环己烯酮和/或γ-丁内酯。通常，产物分布受两个因素控制：（1）亲核试剂的性质和（2）环己酮在C-2和C-4处取代基的空间体积。氢氧化锂诱导的断裂提供丁烯内酯和γ-羟基环己烯酮。相反，在有限的情况下，锂醇盐促进的断裂会导致主要为5取代的γ-丁内酯以及少量的丁烯内酯。由氢氧化锂诱导的裂解产物在很大程度上受环己酮环的C-2和C-4处取代基的空间体积的影响。

  DOI：

  10.1021/jo0490853

文献信息

• Asymmetric synthesis and fragmentation reactions of 2-alkyl- and 2, 4-dialkyl-3-iodo-1-oxocyclohexan-2, 4-carbolactones. Single enantiomer preparation of Δα, β-butenolides, 2-alkyl-4-hydroxy-2-cyclohexen-1-ones and butyrolactones
  作者：Arthur G. Schultz、Mingshi Dai、Seock-Kyu Khim、Liping Pettus、Kshitij Thakkar

  DOI：10.1016/s0040-4039(98)00785-0

  日期：1998.6

  Fragmentation reactions of keto iodolactones 4 provide access to butenolides 5, 2-alkyl-4-hydroxy-2-cyclohexen-1-ones 6, and butyrolactones 9. Delta(alpha,beta)-Butenolides 5e and 5f were converted to heterocycles 14-16 by way of intramolecular cycloaddition reactions. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Asymmetric Total Synthesis of (+)-Apovincamine and a Formal Synthesis of (+)-Vincamine. Demonstration of a Practical “Asymmetric Linkage” between Aromatic Carboxylic Acids and Chiral Acyclic Substrates
  作者：Arthur G. Schultz、William P. Malachowski、You Pan

  DOI：10.1021/jo961603p

  日期：1997.3.1

  Asymmetric syntheses of (+)-apovincamine (1a) and (+)-vincamine (2) are described. Construction of the pentacyclic diene lactam 14, a pivotal intermediate for synthesis of the cis-fused vincane-type alkaloids, began by Birch reduction-alkylation of the chiral benzamide 3 to give the 6-ethyl-1-methoxy-4-methyl-1,4-cyclohexadiene 4. Conversion of 4 to 2,5-cyclohexadienone 5 (92% overall yield from 3) and HPLC analysis of 5 demonstrated the diastereomeric purity resulting from the Birch reduction-alkylation to be >100:1. Dienone 5 was converted to butyrolactone 9 (47% overall yield from 3), and 9 was coupled with tryptamine (10) to give the amide 11a. Amido keto aldehyde 13 was obtained from 11a, and acid-catalyzed tricyclization and subsequent base-induced elimination of MeOH provided the desired cis-fused pentacyclic diene lactam 14. Examination of the two-step process 13 --> 14 revealed a novel base-induced epimerization at C(21) which served to interconvert 14 and 17, possibly by the involvement of a homoenolate. Diene lactam 14 was converted to (+)-apovincaminal 20a, an intermediate in the synthesis of (+)-apovincamine (1a) reported by Winterfeldt and co-workers. A new procedure for conversion of 20a to 1a involves conversion of 20a to the acetal 20b and treatment of 20b with NBS/AIBN in CCl4. The conversion of 1a to vincamine (2) has been reported by Oppolzer and co-workers.
• Novel Fragmentation Reaction of 2-Alkyl- and 2,4-Dialkyl-3-iodo-1-oxocyclohexan-2,4-carbolactones
  作者：Seock-Kyu Khim、Mingshi Dai、Xuqing Zhang、Lei Chen、Liping Pettus、Kshitij Thakkar、Arthur G. Schultz

  DOI：10.1021/jo0490853

  日期：2004.10.1

  2-Alkyl- and 2,4-dialkyl-3-iodo-1-oxocyclohexan-2,4-carbolactones undergo lithium hydroxide- and lithium alkoxide-induced fragmentation reactions to provide butenolides, γ-hydroxycyclohexenones, and/or γ-butyrolactones. In general, product distribution is governed by two factors: (1) the nature of nucleophiles and (2) the steric bulkiness of the substituents at C-2 and C-4 of the cyclohexanones. Lithium

  2-烷基-和2,4-二烷基-3-碘-1-氧代环己基-2,4-碳内酯经历氢氧化锂和烷氧基锂诱导​​的裂解反应，从而提供丁烯内酯，γ-羟基环己烯酮和/或γ-丁内酯。通常，产物分布受两个因素控制：（1）亲核试剂的性质和（2）环己酮在C-2和C-4处取代基的空间体积。氢氧化锂诱导的断裂提供丁烯内酯和γ-羟基环己烯酮。相反，在有限的情况下，锂醇盐促进的断裂会导致主要为5取代的γ-丁内酯以及少量的丁烯内酯。由氢氧化锂诱导的裂解产物在很大程度上受环己酮环的C-2和C-4处取代基的空间体积的影响。