(R)-(+)-5,6-Dihydro-4H-thieno<2,3-b>thiopyran-4-ol 7,7-Dioxide | 131352-46-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 硫吡喃类
• 英文名称: (R)-(+)-5,6-Dihydro-4H-thieno<2,3-b>thiopyran-4-ol 7,7-Dioxide
• 英文别名: (R)-(+)-5,6-Dihydro-4H-thieno[2,3-b]-thiopyran-4-ol-7,7-dioxide；(4R)-7,7-dioxo-5,6-dihydro-4H-thieno[2,3-b]thiopyran-4-ol
• CAS: 131352-46-0
• 化学式: C₇H₈O₃S₂
• 分子量: 204.271
• InChiKey: MFTKAMUOHUPBRG-ZCFIWIBFSA-N

物化性质

• 熔点：
  89-90 °C
• 沸点：
  446.3±45.0 °C(Predicted)
• 密度：
  1.579±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  91
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (R)-(+)-5,6-Dihydro-4H-thieno<2,3-b>thiopyran-4-ol 7,7-Dioxide 在 lithium hexamethyldisilazane 作用下， 反应 2.5h， 生成
  参考文献：
  名称：

  An enantioselective synthesis of the topically-active carbonic anhydrase inhibitor MK-0507: 5,6-dihydro-(S)-4-(ethylamino)-(S)-6-methyl-4H-thieno[2,3-b]thiopyran-2-sulfonamide 7,7-dioxide hydrochloride

  摘要：

  The key feature in the synthesis of topically-active carbonic anhydrase inhibitor MK-0507 (13b) is a Ritter reaction that exhibits an unexpected tendency to proceed with retention of chirality. This phenomenon was further studied on model compounds free from potential diastereomeric effects. A mechanism involving transannular stabilization of the sp2-hybridized center by sulfone oxygen is proposed with the net result of double inversion. A second key feature in the preferred sequence to MK-0507 involves the classic problem of how to maximize substitution over elimination. This problem manifests itself in the stereospecific alkylation of 2-mercaptothiophene with derivatized methyl (R)-3-hydroxybutyrate and is compounded by a subsequent Michael reaction leading to a loss of product chirality. Results are presented that eliminate this problem.

  DOI：

  10.1021/jo00059a013
• 作为产物：
  描述：

  5,6-Dihydro-4H-thieno<2,3-b>thiopyran-4-one 7,7-Dioxide 在 甲酸 、 (S)-RuCl<(1R,2R)-p-TsNCH(C6H5)CH(C6H5)NH2>(η⁶-mesitylene) 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 65.0h， 生成 (R)-(+)-5,6-Dihydro-4H-thieno<2,3-b>thiopyran-4-ol 7,7-Dioxide
  参考文献：
  名称：

  Ruthenium(II)-Catalyzed Asymmetric Transfer Hydrogenation of Ketones Using a Formic Acid−Triethylamine Mixture

  摘要：

  DOI：

  10.1021/ja954126l

文献信息

• Enantioselective Reduction of Ketones and Imines Catalyzed by (CN-Box)ReV-Oxo Complexes
  作者：Kristine A. Nolin、Richard W. Ahn、Yusuke Kobayashi、Joshua J. Kennedy-Smith、F. Dean Toste

  DOI：10.1002/chem.201001164

  日期：2010.8.16

  application of chiral, non‐racemic ReV–oxo complexes to the enantioselective reduction of prochiral ketones is described. In addition to the enantioselective reduction of prochiral ketones, we report the application of these complexes to 1) a tandem Meyer–Schuster rearrangement/reduction to access enantioenriched allylic alcohols and 2) the enantioselective reduction of imines.

  描述了手性非外消旋 Re V - oxo 配合物在前手性酮的对映选择性还原中的开发和应用。除了前手性酮的对映选择性还原外，我们还报告了这些复合物在以下方面的应用：1）串联 Meyer-Schuster 重排/还原以获取对映体富集的烯丙醇和 2）亚胺的对映选择性还原。
• Chiral boron catalysts for reduction of ketones and process for their
  申请人：Merck & Co., Inc.

  公开号：US05189177A1

  公开（公告）日：1993-02-23

  The chiral catalyst of general structure 1, or its enantiomer ##STR1## is prepared by treating the corresponding N-carboxy anhydride of structure 2 ##STR2## with an aryl metal, especially a phenyl metal such as an aryl magnesium halide, aryl lithium, aryl zinc or aryl cesium, to form a 1,1-diaryl- methanol of structure 3 ##STR3## followed by treatment with a compound of structure, 4 ##STR4## The catalyst, wherein R is aromatic, is novel and in some cases superior to the catalyst wherein R is alkyl or aralkyl in directing the chirality of diborane, borane-dimethyl sulfide or borane-tetrahydrofuran reductions of ketones to secondary alcohols.

  一般结构1的手性催化剂，或其对映体##STR1##是通过将相应的结构2的N-羧酸酐用芳基金属，特别是苯基金属，如芳基镁卤化物、芳基锂、芳基锌或芳基铯处理而制备的，以形成结构3的1,1-二芳基甲醇，##STR3##随后用结构4的化合物进行处理。其中R为芳香族，是一种新型催化剂，在某些情况下优于其中R为烷基或芳基烷基的催化剂，能更好地引导二硼烷、硼烷-二甲基硫醚或硼烷-四氢呋喃还原酮为二级醇的手性。
• Chiral catalysts for reduction of ketones and process for their
  申请人：Merck & Co., Inc.

  公开号：US05264585A1

  公开（公告）日：1993-11-23

  The chiral catalyst of general structure 1, or its enantiomer ##STR1## is prepared by treating the corresponding N-carboxy anhydride of structure 2 ##STR2## with an aryl metal, especially a phenyl metal such as an aryl magnesium halide, aryl lithium, aryl zinc or aryl cesium, to form a 1,1-diaryl- methanol of structure 3 ##STR3## followed by treatment with a compound of structure, 4 ##STR4## The catalyst, wherein R is aromatic, is novel and in some cases superior to the catalyst wherein R is alkyl or aralkyl in directing the chirality of diborane, borane-dimethyl sulfide or borane-tetrahydrofuran reductions of ketones to secondary alcohols.

  通用结构1的手性催化剂，或其对映体##STR1##是通过将相应的结构2的N-羧酸酐##STR2##与芳基金属（尤其是苯基金属，如芳基镁卤化物，芳基锂，芳基锌或芳基铯）反应形成结构3的1,1-二芳基甲醇，然后用结构4的化合物进行处理而制备的。其中R为芳香族的催化剂是新颖的，并且在某些情况下比R为烷基或芳基烷基的催化剂更优越，可以指导二硼烷，硼烷-二甲基硫醚或硼烷-四氢呋喃还原酮为二级醇的手性。
• Arylation process for preparation of chiral catalysts for ketone
  申请人：Merck & Co., Inc.

  公开号：US05039802A1

  公开（公告）日：1991-08-13

  The chiral catalyst of general structure 1, or its enantiomer ##STR1## is prepared by treating the corresponding N-carboxy anhydride of structure 2 ##STR2## with an aryl metal, especially a phenyl metal such as an aryl magnesium halide, aryl lithium, aryl zinc or aryl cesium, to form a 1,1-diaryl-methanol of structure 3 ##STR3## followed by treatment with a compound of structure, 4 ##STR4## The catalyst, wherein R is aromatic, is novel and in some cases superior to the catalyst wherein R is alkyl or aralkyl in directing the chirality of borane-dimethyl sulfide reductions of ketones to secondary alcohols.

  一般结构1的手性催化剂，或其对映体##STR1##，是通过用芳基金属（特别是苯基金属，如芳基镁卤、芳基锂、芳基锌或芳基铯）处理相应的结构2的N-羧酸酐##STR2##，形成结构3的1,1-二芳基甲醇，然后用结构4的化合物进行处理而制备的。其中R为芳基的催化剂是新颖的，在某些情况下优于R为烷基或芳基烷基的催化剂，可用于指导硼-二甲基硫醚还原酮为二级醇的手性。
• Chiral catalysts for reduction of ketones and process for their preparation
  申请人：MERCK & CO. INC.

  公开号：EP0453298A2

  公开（公告）日：1991-10-23

  The chiral catalyst of general structure 1, or its enantiomer is prepared by treating the corresponding N-carboxy anhydride of structure 2 with an aryl metal, especially a phenyl metal such as an aryl magnesium halide, aryl lithium, aryl zinc or aryl cesium, to form a 1,1-diaryl- methanol of structure 3 followed by treatment with a compound of structure, 4 The catalyst, wherein R is aromatic, is novel and in some cases superior to the catalyst wherein R is alkyl or aralkyl in directing the chirality of borane-dimethyl sulfide reductions of ketones to secondary alcohols.

  一般结构 1 的手性催化剂或其对映体 或其对映体是通过处理结构 2 中相应的 N-羧基酸酐制备的 用芳基金属，特别是苯基金属，如芳基卤化镁、芳基锂、芳基锌或芳基铯，生成结构 3 的 1,1-二芳基甲醇 然后用结构 4 的化合物处理 该催化剂（其中 R 为芳香族）是一种新型催化剂，在某些情况下优于 R 为烷基或芳烷基的催化剂，可引导硼烷-二甲基硫醚将酮还原成仲醇的手性。