butyl (2S,6S,4Z)-7-(tert-butyldimethylsilyloxy)-2-hydroxy-6-(2-trimethylsilylethoxymethoxy)hept-4-enoate | 172328-25-5

• 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: butyl (2S,6S,4Z)-7-(tert-butyldimethylsilyloxy)-2-hydroxy-6-(2-trimethylsilylethoxymethoxy)hept-4-enoate
• 英文别名: butyl (Z,2S,6S)-7-[tert-butyl(dimethyl)silyl]oxy-2-hydroxy-6-(2-trimethylsilylethoxymethoxy)hept-4-enoate
• CAS: 172328-25-5
• 化学式: C₂₃H₄₈O₆Si₂
• 分子量: 476.802
• InChiKey: IBRNHHDKKPYEFR-WVBBQCPNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.36
• 重原子数：
  31
• 可旋转键数：
  18
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  74.2
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  butyl (2S,6S,4Z)-7-(tert-butyldimethylsilyloxy)-2-hydroxy-6-(2-trimethylsilylethoxymethoxy)hept-4-enoate 在 sodium tetrahydroborate 、 二正丁基氧化锡 、 三乙胺 作用下， 以 乙醇 为溶剂， 反应 37.0h， 生成 (2S,6S,4Z)-7-(tert-butyldimethylsilyloxy)-2-hydroxy-6-(2-trimethylsilylethoxymethoxy)hept-4-enyl toluene-p-sulfonate
  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：

  (4S)-5-(tert-butyldimethylsilyloxy)-4-(2-trimethylsilylethoxymethoxy)pent-2-enyl(tributyl)stannane 、 乙醛酸正丁酯 在 四氯化锡 作用下， 生成 butyl (2S,6S,4Z)-7-(tert-butyldimethylsilyloxy)-2-hydroxy-6-(2-trimethylsilylethoxymethoxy)hept-4-enoate
  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.