(+)-<5(S),S(R)> methyl 3-oxo-5-hydroxy-6-(p-tolylsulfinyl) hexanoate | 171523-67-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (+)-<5(S),S(R)> methyl 3-oxo-5-hydroxy-6-(p-tolylsulfinyl) hexanoate
• 英文别名: (+)-<5(S),S(R)>-Methyl 5-hydroxy-3-oxo-6-(p-tolylsulfinyl)hexanoate；methyl (+)-(5S,SR)-5-hydroxy-3-oxo-6-(p-toluenesulfinyl)hexanoate；methyl (5S)-5-hydroxy-6-[(R)-(4-methylphenyl)sulfinyl]-3-oxohexanoate
• CAS: 171523-67-4
• 化学式: C₁₄H₁₈O₅S
• 分子量: 298.36
• InChiKey: NUKVKHGBBUPNRW-FKIZINRSSA-N

物化性质

• 沸点：
  504.0±50.0 °C(Predicted)
• 密度：
  1.29±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  20
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  99.9
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (+)-<5(S),S(R)> methyl 3-oxo-5-hydroxy-6-(p-tolylsulfinyl) hexanoate 在 4 A molecular sieve 、 二乙基甲氧基硼烷 、 镍 、 zinc(II) chloride 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 15.75h， 生成 (4R,6R)-4-羟基-6-甲基四氢-2H-吡喃-2-酮
  参考文献：
  名称：

  Enantioselective Synthesis of the Unsymmetrical Bis(lactone) (−)-(3E,6R,9E,12S,14R)-Colletol Induced by Chiral Sulfoxides and an Approach to (+)-Colletodiol by Asymmetric Hydroxylation of an α,β-Hydroxy Lactone

  摘要：

  A general synthetic strategy towards the two bis(lactones) (-)-colletol (1) and (+)-colletodiol (2) is described. A common intermediate in this synthesis is the 6-membered hydroxy lactone (+)-(3R,SR)-3-hydroxy-5-hexanolide (6), readily prepared by stereoselective reduction of (+)-(SR)-methyl 3,5-dioxo -6-(p-toluenesulfinyl)hexanoate (7). Stereoselective hydroxylation of this hydroxy lactone has allowed efficient access to (+)-colletodiol(2).

  DOI：

  10.1002/(sici)1099-0690(200001)2000:2<357::aid-ejoc357>3.0.co;2-n
• 作为产物：
  描述：

  (-)-menthyl p-toluenesulfinate 在 叔丁基锂 、 sodium hydride 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 2.75h， 生成 (+)-<5(S),S(R)> methyl 3-oxo-5-hydroxy-6-(p-tolylsulfinyl) hexanoate
  参考文献：
  名称：

  不对称合成中的手性亚砜：（-）-（5S，7R）-茶arch糖内酯的对映选择性合成

  摘要：

  描述了（-）-（5S，7R）-土生黄花内酯的对映选择性合成，该化合物是从菊科植物中分离出来的取代δ-内酯。这种短暂合成的主要特征是立体选择性地还原了β，δ-二酮亚砜，可分6个步骤提供分子的手性中心部分，即syn-1,3-二醇单元。

  DOI：

  10.1016/0957-4166(96)00292-3

文献信息

• Enantioselective synthesis of a bicyclic ketal induced by chiral sulfoxides: (−)-(1R, 3R, 5S)-endo-1,3-dimethyl-2,9-dioxabicyclo-[3,3,1]-nonane
  作者：Guy Solladié、Nathalie Huser

  DOI：10.1016/0957-4166(95)00356-t

  日期：1995.11

  The bicyclic ketal, (-)-(1R,3R,5S)-1,3-dimethyl-2,9-dioxabicyclo-[3,3,1]-nonane, was prepared by a short enantioselective reduction of an enantiomerically pure beta,delta-diketosulfoxide.
• New insights into the reduction of β,δ-diketo-sulfoxides
  作者：Gilles Hanquet、Xavier J. Salom-Roig、Laurence Gressot-Kempf、Steve Lanners、Guy Solladié

  DOI：10.1016/s0957-4166(03)00125-3

  日期：2003.5

  New developments in the reduction of beta,delta-diketo-sulfoxides, a reaction that affords important key intermediates for total synthesis, are described. We showed without ambiguity using NMR experiments, that the beta-carbonyl group is totally enolised. This result is inconsistent with the previous hypothesis, which supposed the other tautomer (enolisation at the delta-position) as the major one. We propose a rationale to explain the side reactions occurring during the reduction of unprotected beta,delta-diketo-sulfoxides and showed that judicious protection of the delta-carbonyl group gave all diastereoisomers of beta-hydroxy-delta-ketosulfoxides. (C) 2003 Elsevier Science Ltd. All rights reserved.
• Chiral Sulfoxides in Asymmetric Synthesis: Enantioselective Synthesis of the Lactonic Moiety of (+)-Compactin and (+)-Mevinolin. Application to a Compactin Analog
  作者：Guy Solladie、Claude Bauder、Leucio Rossi

  DOI：10.1021/jo00129a018

  日期：1995.12

  The lactonic part of (+)-compactin and (+)-mevinolin as well as a compactin analogue were synthesized in an enantioselective way from a beta,delta-diketo sulfoxide easily obtained by the reaction of the trianion of methyl 3,5-dioxohexanoate with (-)-menthyl (S)-p-toluenesulfinate. The main reaction was the two-step stereoselective reduction of beta,delta-diketo sulfoxide without any protective group.
• Enantioselective Synthesis of the Unsymmetrical Bis(lactone) (−)-(3E,6R,9E,12S,14R)-Colletol Induced by Chiral Sulfoxides and an Approach to (+)-Colletodiol by Asymmetric Hydroxylation of an α,β-Hydroxy Lactone
  作者：Guy Solladié、Laurence Gressot、Françoise Colobert

  DOI：10.1002/(sici)1099-0690(200001)2000:2<357::aid-ejoc357>3.0.co;2-n

  日期：2000.1

  A general synthetic strategy towards the two bis(lactones) (-)-colletol (1) and (+)-colletodiol (2) is described. A common intermediate in this synthesis is the 6-membered hydroxy lactone (+)-(3R,SR)-3-hydroxy-5-hexanolide (6), readily prepared by stereoselective reduction of (+)-(SR)-methyl 3,5-dioxo -6-(p-toluenesulfinyl)hexanoate (7). Stereoselective hydroxylation of this hydroxy lactone has allowed efficient access to (+)-colletodiol(2).
• Chiral sulfoxides in asymmetric synthesis: Enantioselective synthesis of (−)-(5S,7R)-Tarchonanthuslactone
  作者：Guy Solladié、Laurence Gressot-Kempf

  DOI：10.1016/0957-4166(96)00292-3

  日期：1996.8

  The enantioselective synthesis of (−)-(5S,7R)-Tarchonanthuslactone, a substituted δ-lactone isolated from a compositae, is described. The main feature of this short synthesis is the stereoselective reduction of a β,δ-diketosulfoxide affording in 6 steps the chiral central part of the molecule, a syn-1,3-diol unit.

  描述了（-）-（5S，7R）-土生黄花内酯的对映选择性合成，该化合物是从菊科植物中分离出来的取代δ-内酯。这种短暂合成的主要特征是立体选择性地还原了β，δ-二酮亚砜，可分6个步骤提供分子的手性中心部分，即syn-1,3-二醇单元。