(2S,6S,3Z)-6,7-epoxy-2-(trimethylsilylethoxymethoxy)hept-3-en-1-ol | 172328-15-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 环氧化物
• 英文名称: (2S,6S,3Z)-6,7-epoxy-2-(trimethylsilylethoxymethoxy)hept-3-en-1-ol
• 英文别名: (Z,2S)-5-[(2S)-oxiran-2-yl]-2-(2-trimethylsilylethoxymethoxy)pent-3-en-1-ol
• CAS: 172328-15-3
• 化学式: C₁₃H₂₆O₄Si
• 分子量: 274.433
• InChiKey: MYPAIAXLKCZYIF-AIMRDXAKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.02
• 重原子数：
  18
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  51.2
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  溴甲苯 、 (2S,6S,3Z)-6,7-epoxy-2-(trimethylsilylethoxymethoxy)hept-3-en-1-ol 在 四丁基碘化铵 、 sodium hydride 作用下， 生成 (2S,6S,3Z)-1-benzyloxy-6,7-epoxy-2-(2-trimethylsilylethoxymethoxy)hept-3-ene
  参考文献：
  名称：

  Stereoselective synthesis of cis- and trans-2,6-disubstituted 5,6-dihydro-2H-pyrans based on 1,5-asymmetric induction in reactions between allylstannanes and aldehydes promoted by tin(IV) chloride

  摘要：

  The allyltin trichloride formed by treating [(4S)-5-(tert-butyldimethylsilyloxy)-4-(2-trimethylsilylethoxy methoxy)]pent-2-enyl(tributyl)stannane 9 with tin(IV) chloride, reacts stereoselectively with 2-oxoethyl toluene-p-sulfonate to give the syn-6-(2-trimethylsilylethoxymethoxy)hept-4-en-2-ol 10 which was converted into the epoxide 11 by treatment with potassium carbonate in methanol. After replacing the tert-butyldimethylsilyl ether by a benzyl ether, removal of the 2-trimethylsilylethoxymethoxy group using trifluoroacetic acid, gave the 2,6-cis- and 2,6-trans-disubstituted 5,6-dihydro-2H-pyrans 14 and 15, ratio 80:20, which were separated as their tert-butyldimethylsilyl ethers 16 and 17 and characterised as their acetates 18 and 19. The 5,6-dihydro-2H-pyrans 24 and 26, ratio 80:20, were similarly prepared from (4S)-4-(2- trimethylsilylethoxymethoxy)pent-2-enyl(tributyl)stannane 21. A complementary route to the trans-2,6-disubstituted 5,6-dihydro-2H-pyran 15 was developed from 2-oxoethyl benzoate which gave the syn-hydroxy ether 28 under the usual conditions. Mesylation and ester saponification gave the anti-epoxide 30 and, after replacing the tert-butyldimethylsilyl ether by a benzyl ether, treatment with trifluoroacetic acid gave the 5,6-dihydro-2H-pyrans 14 and 15, in favour of the trans-isomer, ratio 14:15 = 20:80. Improved stereoselectivity in these dihydropyran syntheses was obtained if the stannane 9 was treated with butyl glyoxylate in the first step. The cis-2,6-disubstituted 5,6-dihydro-2H-pyran 16 was converted into the tetrahydropyran-3-one 37 by hydroboration-oxidation, and into the tetrahydropyran-4-one 43 by treatment with bromine water, reductive debromination and oxidation.

  DOI：

  10.1039/p19950002487
• 作为产物：
  描述：

  (2S,6S,4Z)-7-(tert-butyldimethylsilyloxy)-6-(2-trimethylsilylethoxymethoxy)hept-4-ene-1,2-diol 在 四丁基氟化铵 、 二正丁基氧化锡 、 potassium carbonate 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 55.0h， 生成 (2S,6S,3Z)-6,7-epoxy-2-(trimethylsilylethoxymethoxy)hept-3-en-1-ol
  参考文献：
  名称：

  Stereoselective synthesis of cis- and trans-2,6-disubstituted 5,6-dihydro-2H-pyrans based on 1,5-asymmetric induction in reactions between allylstannanes and aldehydes promoted by tin(IV) chloride

  摘要：

  The allyltin trichloride formed by treating [(4S)-5-(tert-butyldimethylsilyloxy)-4-(2-trimethylsilylethoxy methoxy)]pent-2-enyl(tributyl)stannane 9 with tin(IV) chloride, reacts stereoselectively with 2-oxoethyl toluene-p-sulfonate to give the syn-6-(2-trimethylsilylethoxymethoxy)hept-4-en-2-ol 10 which was converted into the epoxide 11 by treatment with potassium carbonate in methanol. After replacing the tert-butyldimethylsilyl ether by a benzyl ether, removal of the 2-trimethylsilylethoxymethoxy group using trifluoroacetic acid, gave the 2,6-cis- and 2,6-trans-disubstituted 5,6-dihydro-2H-pyrans 14 and 15, ratio 80:20, which were separated as their tert-butyldimethylsilyl ethers 16 and 17 and characterised as their acetates 18 and 19. The 5,6-dihydro-2H-pyrans 24 and 26, ratio 80:20, were similarly prepared from (4S)-4-(2- trimethylsilylethoxymethoxy)pent-2-enyl(tributyl)stannane 21. A complementary route to the trans-2,6-disubstituted 5,6-dihydro-2H-pyran 15 was developed from 2-oxoethyl benzoate which gave the syn-hydroxy ether 28 under the usual conditions. Mesylation and ester saponification gave the anti-epoxide 30 and, after replacing the tert-butyldimethylsilyl ether by a benzyl ether, treatment with trifluoroacetic acid gave the 5,6-dihydro-2H-pyrans 14 and 15, in favour of the trans-isomer, ratio 14:15 = 20:80. Improved stereoselectivity in these dihydropyran syntheses was obtained if the stannane 9 was treated with butyl glyoxylate in the first step. The cis-2,6-disubstituted 5,6-dihydro-2H-pyran 16 was converted into the tetrahydropyran-3-one 37 by hydroboration-oxidation, and into the tetrahydropyran-4-one 43 by treatment with bromine water, reductive debromination and oxidation.

  DOI：

  10.1039/p19950002487

文献信息

• Stereoselective synthesis of cis- and trans-2,6-disubstituted 5,6-dihydro-2H-pyrans based on 1,5-asymmetric induction in reactions between allylstannanes and aldehydes promoted by tin(IV) chloride
  作者：Robert J. Maguire、Eric J. Thomas

  DOI：10.1039/p19950002487

  日期：——

  The allyltin trichloride formed by treating [(4S)-5-(tert-butyldimethylsilyloxy)-4-(2-trimethylsilylethoxy methoxy)]pent-2-enyl(tributyl)stannane 9 with tin(IV) chloride, reacts stereoselectively with 2-oxoethyl toluene-p-sulfonate to give the syn-6-(2-trimethylsilylethoxymethoxy)hept-4-en-2-ol 10 which was converted into the epoxide 11 by treatment with potassium carbonate in methanol. After replacing the tert-butyldimethylsilyl ether by a benzyl ether, removal of the 2-trimethylsilylethoxymethoxy group using trifluoroacetic acid, gave the 2,6-cis- and 2,6-trans-disubstituted 5,6-dihydro-2H-pyrans 14 and 15, ratio 80:20, which were separated as their tert-butyldimethylsilyl ethers 16 and 17 and characterised as their acetates 18 and 19. The 5,6-dihydro-2H-pyrans 24 and 26, ratio 80:20, were similarly prepared from (4S)-4-(2- trimethylsilylethoxymethoxy)pent-2-enyl(tributyl)stannane 21. A complementary route to the trans-2,6-disubstituted 5,6-dihydro-2H-pyran 15 was developed from 2-oxoethyl benzoate which gave the syn-hydroxy ether 28 under the usual conditions. Mesylation and ester saponification gave the anti-epoxide 30 and, after replacing the tert-butyldimethylsilyl ether by a benzyl ether, treatment with trifluoroacetic acid gave the 5,6-dihydro-2H-pyrans 14 and 15, in favour of the trans-isomer, ratio 14:15 = 20:80. Improved stereoselectivity in these dihydropyran syntheses was obtained if the stannane 9 was treated with butyl glyoxylate in the first step. The cis-2,6-disubstituted 5,6-dihydro-2H-pyran 16 was converted into the tetrahydropyran-3-one 37 by hydroboration-oxidation, and into the tetrahydropyran-4-one 43 by treatment with bromine water, reductive debromination and oxidation.