bis(2-chloroallyl) carbonate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机碳酸及其衍生物
• 英文名称: bis(2-chloroallyl) carbonate
• 英文别名: dichloroallyl carbonate；2-chloroallyl carbonate；Bis(2-chloroprop-2-enyl) carbonate
• 化学式: C₇H₈Cl₂O₃
• 分子量: 211.045
• InChiKey: BHFOWOVSFVIOMU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  12
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  bis(2-chloroallyl) carbonate 、 3-异丁氧基-2-环己烯酮 在 lithium diisopropyl amide 作用下， 以 甲苯 为溶剂， 以31%的产率得到
  参考文献：
  名称：

  A general enantioselective route to the chamigrene natural product family

  摘要：

  Described in this report is an enantioselective route toward the chamigrene natural product family. The key disconnections in our synthetic approach include sequential enantioselective decarboxylative allylation and ring-closing olefin metathesis to form the all-carbon quaternary stereocenter and spirocyclic core present in all members of this class of compounds. The generality of this strategy is demonstrated by the first total syntheses of elatol and the proposed structure of laurencenone B, as well as the first enantioselective total syntheses of laurencenone C and alpha-chamigrene. A brief exploration of the substrate scope of the enantioselective decarboxylative allylation/ring-closing metathesis sequence with fully substituted vinyl chlorides is also presented. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2010.04.128

文献信息

• Enantioselective Decarboxylative Alkylation Reactions: Catalyst Development, Substrate Scope, and Mechanistic Studies
  作者：Douglas C. Behenna、Justin T. Mohr、Nathaniel H. Sherden、Smaranda C. Marinescu、Andrew M. Harned、Kousuke Tani、Masaki Seto、Sandy Ma、Zoltán Novák、Michael R. Krout、Ryan M. McFadden、Jennifer L. Roizen、John A. Enquist、David E. White、Samantha R. Levine、Krastina V. Petrova、Akihiko Iwashita、Scott C. Virgil、Brian M. Stoltz

  DOI：10.1002/chem.201003383

  日期：2011.12.9

  functions with nearly identical efficiency in terms of yield and enantioselectivity. Catalyst discovery and development, the optimization of reaction conditions, the exploration of reaction scope, and applications in target‐directed synthesis are reported. Experimental observations suggest that these alkylation reactions occur through an unusual inner‐sphere mechanism involving binding of the prochiral

  在钯配合物与各种膦恶唑啉 (PHOX) 配体的存在下，通过不稳定的前手性烯醇化亲核试剂对烯丙基和炔丙基亲电子试剂进行新颖的对映选择性烷基化来获得 α-季酮。三类烯醇化物前体获得了优异的产率和高对映体过量：烯醇碳酸酯、烯醇硅烷和外消旋 β-酮酯。这些底物类别中的每一种在产率和对映选择性方面都具有几乎相同的效率。报道了催化剂的发现和开发、反应条件的优化、反应范围的探索以及在靶向合成中的应用。实验观察表明，这些烷基化反应通过一种不寻常的内球机制发生，涉及前手性烯醇化亲核试剂直接与钯中心结合。
• Catalytic Enantioselective Alkylation of Substituted Dioxanone Enol Ethers: Ready Access to C(α)-Tetrasubstituted Hydroxyketones, Acids, and Esters
  作者：Masaki Seto、Jennifer L. Roizen、Brian M. Stoltz

  DOI：10.1002/anie.200801424

  日期：2008.8.25

  The catalytic enantioselective formation of tetrasubstituted α-alkoxycarbonyl compounds is an ongoing challenge to synthetic chemists.[1] Fully-substituted α-hydroxyesters and acids comprise essential components of, and building blocks for, many bioactive natural products. These include quinic acid (1), cytotoxic leiodolide A (2),[2] and the anti-cancer agents in the harringtonine series (3a–f), whose activities depend dramatically on the presence and composition of an α-hydroxyester side-chain.[3] While many approaches to these important moieties exist,[4,5] we envisioned applying our recently developed palladium-catalyzed methods for the formation of enantioenriched all-carbon quaternary stereocenters in cyclic alkanones[6] to a general synthesis of C(α)-tetrasubstituted hydroxy carbonyl compounds.[7]
• Deracemization of Quaternary Stereocenters by Pd-Catalyzed Enantioconvergent Decarboxylative Allylation of Racemic β-Ketoesters
  作者：Justin T. Mohr、Douglas C. Behenna、Andrew M. Harned、Brian M. Stoltz

  DOI：10.1002/anie.200502018

  日期：2005.10.28