tert-Butyl-[(1R,2R)-1-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl)-2-methyl-but-3-enyloxy]-dimethyl-silane | 208583-63-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: tert-Butyl-[(1R,2R)-1-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl)-2-methyl-but-3-enyloxy]-dimethyl-silane
• 英文别名: tert-butyl-[(1R,2R)-1-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2-methylbut-3-enoxy]-dimethylsilane
• CAS: 208583-63-5
• 化学式: C₁₆H₃₂O₃Si
• 分子量: 300.514
• InChiKey: YNIKHEKNEXUGMV-MGPQQGTHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.35
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  tert-Butyl-[(1R,2R)-1-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl)-2-methyl-but-3-enyloxy]-dimethyl-silane 在 二甲基硫 、 二异丁基氢化铝 、 臭氧 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 (4R,5R,E)-5-{[(tert-butyl)dimethylsilyl]oxy}-5-[(R)-2,2-dimethyl-1,3-dioxolan-4-yl]-4-methylpent-2-en-1-ol
  参考文献：
  名称：

  An efficient protocol for the stereoselective dihydroxylation of ene-ester systems

  摘要：

  Dihydroxylation of ene ester systems was achieved in good yield and diastereoselectivity under classical catalytic OsO4 and NMO conditions using the intrinsic diastereoselectivity in alpha-methyl beta-OTBS systems. This intrinsic diastereoselection can be reversed using 'super' AD-mix to give the opposite diastereomer also in good selectivity. The regioselection of dihydroxylation in diene esters using a modified 'super' AD-mix was poor. This methodology can be applied towards the synthesis of part structures of the marine macrolide Altohyrtin A. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(98)00800-x
• 作为产物：
  描述：

  (R)-(+)-2,2-二甲基-1,3-二氧戊环-4-甲醛 在 咪唑 、 盐酸 、 正丁基锂 、 硼酸三异丙酯 、 4 Angstroem MS 、 potassium tert-butylate 、 D-(-)-酒石酸二异丙酯 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 0.42h， 生成 tert-Butyl-[(1R,2R)-1-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl)-2-methyl-but-3-enyloxy]-dimethyl-silane
  参考文献：
  名称：

  An efficient protocol for the stereoselective dihydroxylation of ene-ester systems

  摘要：

  Dihydroxylation of ene ester systems was achieved in good yield and diastereoselectivity under classical catalytic OsO4 and NMO conditions using the intrinsic diastereoselectivity in alpha-methyl beta-OTBS systems. This intrinsic diastereoselection can be reversed using 'super' AD-mix to give the opposite diastereomer also in good selectivity. The regioselection of dihydroxylation in diene esters using a modified 'super' AD-mix was poor. This methodology can be applied towards the synthesis of part structures of the marine macrolide Altohyrtin A. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(98)00800-x

文献信息

• A novel fluoride induced cyclisation reaction
  作者：Stephen A. Hermitage、Stanley M. Roberts

  DOI：10.1016/s0040-4039(98)00549-8

  日期：1998.5

  reversed to a 1:8 selectivity by the use of Sharpless AD technology. The acetonides 9 and 10 could be elaborated to ene ester systems 12 and 14 respectively. Both 12 and 14 underwent a peculiar cyclisation reaction to furnish the 5,5-fused ring systems 13 and 15.

  8的OsO 4二羟基化中的固有非对映选择性产生了12：1的立体异构体混合物，可通过使用Sharpless AD技术将其转换为1：8的选择性。的丙酮化合物9和10可以被精制成烯酯系统12和14分别。两个12和14经历了一个特殊的环化反应，得到的5,5-稠合环系统13和15。