(+/-)-(1S*,4R*,5R*)-1,2,3,4-tetrachloro-5-hydroxymethylbicyclo<2.2.1>hept-2-en-7-one dimethylketal | 38460-82-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+/-)-(1S*,4R*,5R*)-1,2,3,4-tetrachloro-5-hydroxymethylbicyclo<2.2.1>hept-2-en-7-one dimethylketal
• 英文别名: rac-((1S,2S,4R)-1,4,5,6-tetrachloro-7,7-dimethoxybicyclo[2.2.1]hept-5-en-2-yl)methanol；rac-1,4,5,6-tetrachloro-2-(hydroxymethyl)-7,7-dimethoxybicyclo[2.2.1]-hept-5-ene；2-endo-hydroxymethyl-1,4,5,6-tetrachloro-7,7-dimethoxybicyclo[2.2.1]hept-5-ene；(+/-)-(1S*,4R*,5R*)-1,2,3,4-tetrachloro-5-hydroxymethylbicyclo[2.2.1]hept-2-en-7-one dimethylketal；[(1R,2R,4S)-1,4,5,6-tetrachloro-7,7-dimethoxy-2-bicyclo[2.2.1]hept-5-enyl]methanol
• CAS: 38460-82-1；117514-74-6；123559-57-9
• 化学式: C₁₀H₁₂Cl₄O₃
• 分子量: 322.015
• InChiKey: RHZMKFKNXXSAMT-CGMLFGJQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+/-)-(1S*,4R*,5R*)-1,2,3,4-tetrachloro-5-hydroxymethylbicyclo<2.2.1>hept-2-en-7-one dimethylketal 在 ruthenium trichloride 、 sodium hydroxide 、 sodium periodate 作用下， 以 甲醇 、 乙醚 、 水 、 乙腈 为溶剂， 反应 2.0h， 生成 methyl 5,6a-dichloro-6,6-dimethoxy-1-oxohexahydrocyclopenta[c]furan-5-carboxylate
  参考文献：
  名称：

  An Easy Access to γ-Lactone-Fused Cyclopentanoids

  摘要：

  The tricyclic alpha-keto hemiacetals 3a,b and 8a-d obtained from ruthenium-catalyzed oxidation of tetrahalonorbornyl derivatives possessing a pendant hydroxymethyl group were cleaved using Pb-(OAc)(4) or alkaline H2O2 to give gamma-lactone-fused cyclopentane derivatives 5a,b and 9a-d. The a-keto hemiacetal 3b has also been elaborated to spiroepoxide derivative 25. The stable hydrate 4 formed from ruthenium-catalyzed oxidation of acrolein adduct 10 furnished an intramolecular hemiacetal 11 upon cleavage with Pb(OAc)(4). The alpha-halo ester moiety in 5a was transformed smoothly in a highly regio- and stereoselective manner to alpha-hydroxy esters through a lactone-assisted intermediate to furnish 18.

  DOI：

  10.1021/jo025521e
• 作为产物：
  描述：

  5,5-二甲氧基-1,2,3,4-四氯环戊二烯 、 烯丙醇 反应 50.0h， 生成 (+/-)-(1S*,4R*,5R*)-1,2,3,4-tetrachloro-5-hydroxymethylbicyclo<2.2.1>hept-2-en-7-one dimethylketal
  参考文献：
  名称：

  两种新型Carbasugar衍生物的酶催化立体选择性合成

  摘要：

  外消旋1,4,5,6-四氯-2-（羟甲基）的酶拆分-7,7-二甲氧基二环[2.2.1]庚-5-烯（外消旋- 1）在乙酸乙烯酯使用各种脂肪酶如乙酰基源是研究过。获得的对映体富集（+）-（1,4,5,6-四氯-7,7-二甲氧基双环[2.2.1]庚-5-烯-2-基）乙酸甲酯（（+）- 2 ; 94％ ee），先在液态NH 3中用Na处理，然后在丙酮中用Amberlyst-15树脂处理，得到（−）-5-（羟甲基）双环[2.2.1]庚-2-烯-7-酮（（-） ‐ 7），它是合成羧甲基蔗糖衍生物的宝贵前体。随后的拜尔·维利格氧化得到不可分离的双环内酯混合物，将其进行LiAlH 4还原，然后乙酰化。将生成的化合物（−）- 11和（+）‐ 12进行顺式羟化反应，然后进行乙酰化反应，得到新的羧甲基糖衍生物（1 S，2 R，3 S，4 S，5 S） 4,5-双（乙酰氧基甲基）环己烷-1,2,3-三乙酸三酯（（-）-（13））和（1

  DOI：

  10.1002/hlca.201000213

文献信息

• A Ruthenium-Catalyzed, Novel and Facile Procedure for the Conversion of Vicinal Dihaloalkenes to α-Diketones
  作者：Faiz Ahmed Khan、B. Prabhudas、Jyotirmayee Dash、Nilam Sahu

  DOI：10.1021/ja001956c

  日期：2000.10.1

  transition metal chemistry, used in the preparation of variety of heterocycles and natural products. α-Diketones also function as the key elements in the Weiss reaction and in the construction of rigid molecular assemblies (molecular wires, rods, etc.) based on ‘block’ chemistry. Some of the common methods to obtain α-diketones are: (i) oxidation of αhydroxyketones, (ii) oxidation of alkynes, and (iii)

  丰富的官能团以及在各种键形成反应中创建、相互转化和利用它们的大量方法是设计任何目标分子化学合成的重要资产。α-二酮是两个相邻羰基的强大组合，由于其广泛的应用而备受关注。α-二酮表现出有趣的光化学，用作调味剂，用作过渡金属化学中配体的前体，用于制备各种杂环和天然产物。α-二酮也是 Weiss 反应和基于“嵌段”化学的刚性分子组件（分子线、棒等）的构建中的关键元素。获得 α-二酮的一些常用方法是： (i) α-羟基酮的氧化，(ii) 炔烃的氧化，和 (iii) α-亚甲基酮的氧化。尽管烯烃的受控氧化很困难，但据报道，KMnO4/Ac2O 会产生低到中等产率的 α-二酮和副产物。但是，该方法不适用于小环（环辛烯以下）和双环系统。我们发现，邻位二卤代烯烃可以作为掩蔽的 α-二酮（方案 1）。我们特别选择了
• Ruthenium-Mediated Oxidation under Buffered Conditions: A Simple and Useful Protocol for the Synthesis of Norbornyl α-Diketones with Acid Sensitive Functionalities
  作者：Faiz Ahmed Khan、Ch. Sudheer

  DOI：10.1002/adsc.200900042

  日期：2009.4

  Abstractmagnified imageThe supported ruthenium‐catalyzed oxidation of the 1,2‐dihaloalkene moiety in tetrahalonorbornyl derivatives possessing acid labile functionalities to afford the corresponding α‐diketones is demonstrated. The protocol was successfully applied in the synthesis of a cyclopenta‐annulated δ‐lactone derived from D‐mannitol.
• Synthesis of 1,4,5,6-tetrachloro-7,7-dimethoxybicyclo[2.2.1]hept-5-enylmethyl haloacetates
  作者：T. G. Kyazymova、E. G. Mamedbeili、O. B. Abdiev、Z. M. Nagiev、S. T. Alieva、A. V. Nagiev

  DOI：10.1134/s1070427209010194

  日期：2009.1

  The possibility of preparing 1,4,5,6-tetrachloro-7,7-dimethoxybicyclo[2.2.1] hept-5-enylmethyl haloacetates by the reaction of tetrachlorodimethoxycyclopentadiene with allyl haloacetates was examined. The effect of various factors on the product yield was studied, and the optimal synthesis conditions were found.
• A versatile regio- and stereospecific annulation method - I
  作者：Edda Gössinger、Renate Müller

  DOI：10.1016/0040-4020(89)80136-x

  日期：1989.1
• Stereoselective synthesis of γ-lactone fused cyclopentanoids
  作者：Ayşegül Gümüş、Cihangir Tanyeli

  DOI：10.1016/j.tetasy.2012.09.010

  日期：2012.10

  The stereoselective synthesis of gamma-lactone fused cyclopentanoids applying chemoenzymatic methods is described. rac-2-Hydroxymethyl-1,4,5,6-tetrachloro-7,7-dimethoxybicyclo[2.2.1]hept-5-ene and rac-2-hydroxymethyl-1,4,5,6,7,7-hexachlorobicyclo[2.2.1]hept-5-ene were successfully resolved by Candida rugosa lipase (CRL), to afford enantiomerically enriched products with an ee of 94 and 97%, respectively. The enantiomerically enriched acetates were then subjected to ruthenium and/or cerium catalyzed oxidation to afford alpha-diketones and subsequent alkaline H2O2 mediated oxidative cleavage reaction of alpha-diketones, followed by CH2N2 esterification, gave enantiomerically enriched gamma-lactone fused cyclopentanoids with known absolute configurations. (C) 2012 Elsevier Ltd. All rights reserved.