(4'aS,5'S)-4',4'a,5',6',7',8'-hexahydro-5'-<oxy>-4a'-methylspiro<1,3-dithiolane-2,2'(3'H)-naphthalene>-5'-carbonitrile | 145632-91-3

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫代缩醛
• 英文名称: (4'aS,5'S)-4',4'a,5',6',7',8'-hexahydro-5'-<oxy>-4a'-methylspiro<1,3-dithiolane-2,2'(3'H)-naphthalene>-5'-carbonitrile
• 英文别名: (1'S,8'aS)-1'-[tert-butyl(dimethyl)silyl]oxy-8'a-methylspiro[1,3-dithiolane-2,6'-3,4,7,8-tetrahydro-2H-naphthalene]-1'-carbonitrile
• CAS: 145632-91-3
• 化学式: C₂₀H₃₃NOS₂Si
• 分子量: 395.706
• InChiKey: BASULORHBIBQFL-RBUKOAKNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.36
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  83.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (4'aS,5'S)-4',4'a,5',6',7',8'-hexahydro-5'-<oxy>-4a'-methylspiro<1,3-dithiolane-2,2'(3'H)-naphthalene>-5'-carbonitrile 在 thallium(III) nitrate 作用下， 以 四氢呋喃 、 甲醇 、 氯仿 为溶剂， 反应 0.33h， 以82%的产率得到(1S,8aS)-1,2,3,4,8,8a-hexahydro-1-<oxy>-8a-methyl-6(7H)-oxonaphthalene-1-carbonitrile
  参考文献：
  名称：

  Addition of tert-butyldimethyl- or tert-butyldiphenylsilyl cyanide to hindered ketones

  摘要：

  The addition of trimethylsilyl cyanide (TMSCN), tert-butyldimethylsilyl cyanide (TBDMSCN) or tert-butyldiphenylsilyl cyanide (TBDPSCN) to sterically hindered ketones proceeded in good yield under catalysis by Lewis acids (ZnI2, CH2Cl2, 25-degrees-C) or bases (KCN, 18-crown-6, CH2Cl2, 25-degrees-C). For example, the ZnI2-catalyzed addition of TBDMSCN to 2,2-dimethylcyclohexanone (3e), 2,2,6-trimethylcyclohexanone (3f), and 2,2,6,6-tetramethylcyclohexanone (3g) provided the protected cyanohydrins 4e, 4f, and 4g in 94, 83, and 92 % yield, respectively. The C-1 ketone of C-6 dithioketal-protected Wieland-Miescher ketone ((4'aS)-4',4'a,7',8'-tetrahydro-4a'-methylspiro[1,3-dithiolane-2,2'(3'H)-naphthalen]-5'(6'H)-one (+)-(8)) provided (4'aS,5'S)-4',4'a,5',6',7',8'-hexahydro-5'-[(di-methyl(1,1-dimethylethyl)silyl)oxy]-4a'-methylspiro[1,3-dithiolane-2,2'(3'H)-naphthalene]-5'-car-bonitrile (+)-(10b) in 94% yield. An X-ray crystallographic study established that the C-5 center in (+)-10b has the correct absolute stereochemistry needed for a projected synthesis of the C-1 center in the A ring of taxol using (+)-10b as a starting material.

  DOI：

  10.1021/jo00053a030
• 作为产物：
  描述：

  (S)-(+)-3,4,8,8a-四氢-8a-甲基-1,6-(2H,7H)-萘醌 在 对甲苯磺酸 、 zinc(II) iodide 作用下， 以 二氯甲烷 、 溶剂黄146 为溶剂， 生成 (4'aS,5'S)-4',4'a,5',6',7',8'-hexahydro-5'-<oxy>-4a'-methylspiro<1,3-dithiolane-2,2'(3'H)-naphthalene>-5'-carbonitrile
  参考文献：
  名称：

  An enantioselective approach to ring a of taxol using the wieland-miescher ketone

  摘要：

  The selective protection of the S-(+)-enantiomer of the Wieland Miescher ketone (2) as the tertbutyldimethylsilyl-protected cyanohydrin 7 and the oxidative cleavage of an alpha-ketol 8 that was derived from 7 provided a model 10 for the A ring of the taxol (1) possessing the correct C-1 stereochemistry of taxol and functionality suitable for further elaboration.

  DOI：

  10.1016/s0040-4039(00)60056-4

文献信息

• Addition of tert-butyldimethyl- or tert-butyldiphenylsilyl cyanide to hindered ketones
  作者：Miroslaw Golinski、Carolyn P. Brock、David S. Watt

  DOI：10.1021/jo00053a030

  日期：1993.1

  The addition of trimethylsilyl cyanide (TMSCN), tert-butyldimethylsilyl cyanide (TBDMSCN) or tert-butyldiphenylsilyl cyanide (TBDPSCN) to sterically hindered ketones proceeded in good yield under catalysis by Lewis acids (ZnI2, CH2Cl2, 25-degrees-C) or bases (KCN, 18-crown-6, CH2Cl2, 25-degrees-C). For example, the ZnI2-catalyzed addition of TBDMSCN to 2,2-dimethylcyclohexanone (3e), 2,2,6-trimethylcyclohexanone (3f), and 2,2,6,6-tetramethylcyclohexanone (3g) provided the protected cyanohydrins 4e, 4f, and 4g in 94, 83, and 92 % yield, respectively. The C-1 ketone of C-6 dithioketal-protected Wieland-Miescher ketone ((4'aS)-4',4'a,7',8'-tetrahydro-4a'-methylspiro[1,3-dithiolane-2,2'(3'H)-naphthalen]-5'(6'H)-one (+)-(8)) provided (4'aS,5'S)-4',4'a,5',6',7',8'-hexahydro-5'-[(di-methyl(1,1-dimethylethyl)silyl)oxy]-4a'-methylspiro[1,3-dithiolane-2,2'(3'H)-naphthalene]-5'-car-bonitrile (+)-(10b) in 94% yield. An X-ray crystallographic study established that the C-5 center in (+)-10b has the correct absolute stereochemistry needed for a projected synthesis of the C-1 center in the A ring of taxol using (+)-10b as a starting material.
• An enantioselective approach to ring a of taxol using the wieland-miescher ketone
  作者：Miroslaw Golinski、Sundar Vasudevan、Rey Floresca、Carolyn P. Brock、David S. Watt

  DOI：10.1016/s0040-4039(00)60056-4

  日期：1993.1

  The selective protection of the S-(+)-enantiomer of the Wieland Miescher ketone (2) as the tertbutyldimethylsilyl-protected cyanohydrin 7 and the oxidative cleavage of an alpha-ketol 8 that was derived from 7 provided a model 10 for the A ring of the taxol (1) possessing the correct C-1 stereochemistry of taxol and functionality suitable for further elaboration.