4-chloro-2,4-dicyano-2-methyl-thiobutyric acid S-methyl ester | 884631-42-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 4-chloro-2,4-dicyano-2-methyl-thiobutyric acid S-methyl ester
• 英文别名: S-methyl (2S,4R)-4-chloro-2,4-dicyano-2-methylbutanethioate
• CAS: 884631-42-9
• 化学式: C₈H₉ClN₂OS
• 分子量: 216.691
• InChiKey: ARQJPRNPOHMDOS-SVRRBLITSA-N

物化性质

• 沸点：
  370.8±42.0 °C(Predicted)
• 密度：
  1.272±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  90
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-chloro-2,4-dicyano-2-methyl-thiobutyric acid S-methyl ester 在 溶剂黄146 、 锌 作用下， 以 乙醚 为溶剂， 生成 S-methyl (2S)-2,4-dicyano-2-methylbutanethioate
  参考文献：
  名称：

  Control of Diastereoselectivity in Tandem Asymmetric Reactions Generating Nonadjacent Stereocenters with Bifunctional Catalysis by Cinchona Alkaloids

  摘要：

  We report the manipulation of hydrogen-bonding-based cooperative catalysis to control the diastereoselectivity for a tandem asymmetric reaction creating two nonadjacent stereocenters. This ability to control both the enantioselectivity and diastereoselectivity allows, for the first time, the direct and stereoselective construction of 1,3-tertiary-quaternary stereocenters in any of the possible four configurations from the same prochiral precursors with catalytic control. The synthetic consequence of such catalyst-controlled construction of nonadjacent stereocenters is illustrated by the asymmetric synthesis of manzacidin C by using the same reaction sequence that was previously applied to the total synthesis of manzacidin A.

  DOI：

  10.1021/ja0670409
• 作为产物：
  描述：

  S-methyl 2-cyanothiopropionate 、 2-氯丙烯腈 在 N-[3,5-双(三氟甲基)苯基]-N'-[(8a,9S)-6'-甲氧基-9-金鸡宁]硫脲 作用下， 以 甲苯 为溶剂， 反应 12.0h， 生成 4-chloro-2,4-dicyano-2-methyl-thiobutyric acid S-methyl ester 、 4-chloro-2,4-dicyano-2-methyl-thiobutyric acid S-methyl ester 、 S-methyl (2S,4S)-4-chloro-2,4-dicyano-2-methylbutanethioate
  参考文献：
  名称：

  Control of Diastereoselectivity in Tandem Asymmetric Reactions Generating Nonadjacent Stereocenters with Bifunctional Catalysis by Cinchona Alkaloids

  摘要：

  We report the manipulation of hydrogen-bonding-based cooperative catalysis to control the diastereoselectivity for a tandem asymmetric reaction creating two nonadjacent stereocenters. This ability to control both the enantioselectivity and diastereoselectivity allows, for the first time, the direct and stereoselective construction of 1,3-tertiary-quaternary stereocenters in any of the possible four configurations from the same prochiral precursors with catalytic control. The synthetic consequence of such catalyst-controlled construction of nonadjacent stereocenters is illustrated by the asymmetric synthesis of manzacidin C by using the same reaction sequence that was previously applied to the total synthesis of manzacidin A.

  DOI：

  10.1021/ja0670409

文献信息

• Dual-Function Cinchona Alkaloid Catalysis:  Catalytic Asymmetric Tandem Conjugate Addition−Protonation for the Direct Creation of Nonadjacent Stereocenters
  作者：Yi Wang、Xiaofeng Liu、Li Deng

  DOI：10.1021/ja060312n

  日期：2006.3.1

  addition-protonation with efficient catalytic control of two nonadjacent stereocenters. As demonstrated in a concise and highly stereoselective formal total synthesis of (-)-manzacidin A, this asymmetric tandem reaction establishes a new and versatile catalytic approach for the enantioselective and diastereoselective creation of 1,3-tertiary-quaternary stereocenters.

  催化串联不对称反应构成了直接从非手性前体在非环状分子中不对称构建非相邻立体中心的有力策略。在这篇通讯中，我们报告了在双功能金鸡纳生物碱催化剂的催化下，三取代的碳供体对 2-氯丙烯腈的高度对映选择性和非对映选择性加成。这代表了第一个不对称串联共轭加成-质子化，对两个不相邻的立体中心进行有效的催化控制。正如 (-)-manzacin A 的简洁且高度立体选择性的正式全合成所证明的那样，这种不对称串联反应为 1,3-叔-四元立体中心的对映选择性和非对映选择性创建建立了一种新的通用催化方法。
• Asymmetric carbon-carbon-bond-forming reactions catalyzed by bifunctional cinchona alkaloids
  申请人：Deng Li

  公开号：US20070083049A1

  公开（公告）日：2007-04-12

  One aspect of the present invention relates to quinine-based and quinidine-based catalysts. In certain embodiments, the quinine-based and quinidine-based catalysts contain a hydroxy group at the 6′ position. In certain embodiments, the quinine-based and quinidine-based catalysts contain an O-aryl group or an O-aroyl group at the C9 position. In certain embodiments, the quinine-based and quinidine-based catalysts contain an optionally substituted O-diazene group or an optionally substituted O-benzoyl group at the C9 position. In certain embodiments, the quinine-based and quinidine-based catalysts contain a thiourea at the C9 position. In certain embodiments, the quinine-based and quinidine-based catalysts contain an NH(═S)NH-aryl group at the C9 position. Another aspect of the present invention relates to a method of preparing a chiral, non-racemic compound from a prochiral electron-deficient alkene or prochiral imine, comprising the step of: reacting a prochiral alkene or imine with a nucleophile in the presence of a catalyst; thereby producing a chiral, non-racemic compound; wherein said catalyst is a derivatized quinine or quinidine. In certain embodiments, the nucleophile is a malonate or β-ketoester. In certain embodiments the nucleophile is an alkyl or aryl or aralkyl 2-cyano-2-alkylacetate. In certain embodiments the nucleophile is an alkyl or aryl or aralkyl 2-cyano-2-alkylacetate. Another aspect of the present invention relates to a method of kinetic resolution, comprising the step of: reacting a racemic aldehyde or racemic ketone with a nucleophile in the presence of a derivatized quinine or quinidine, thereby producing a non-racemic, chiral compound. In certain embodiments, the kinetic resolution is dynamic.