(E)-(4R,5R)-5-(tert-Butyl-dimethyl-silanyloxy)-5-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl)-4-methyl-pent-2-enoic acid methyl ester | 208583-64-6

• 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: (E)-(4R,5R)-5-(tert-Butyl-dimethyl-silanyloxy)-5-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl)-4-methyl-pent-2-enoic acid methyl ester
• 英文别名: methyl (E,4R,5R)-5-[tert-butyl(dimethyl)silyl]oxy-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-4-methylpent-2-enoate
• CAS: 208583-64-6
• 化学式: C₁₈H₃₄O₅Si
• 分子量: 358.55
• InChiKey: OHTZTUWWEDQAHQ-RQLQGFKTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.89
• 重原子数：
  24
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (E)-(4R,5R)-5-(tert-Butyl-dimethyl-silanyloxy)-5-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl)-4-methyl-pent-2-enoic acid methyl ester 在 二异丁基氢化铝 、 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 为溶剂， 反应 2.5h， 生成 (E)-(4R,5R)-5-(tert-Butyl-dimethyl-silanyloxy)-5-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl)-4-methyl-pent-2-enal
  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 、 二甲基硫 、 硼酸三异丙酯 、 4 Angstroem MS 、 potassium tert-butylate 、 D-(-)-酒石酸二异丙酯 、 臭氧 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.92h， 生成 (E)-(4R,5R)-5-(tert-Butyl-dimethyl-silanyloxy)-5-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl)-4-methyl-pent-2-enoic acid methyl ester
  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。
• Synthesis and biological activity of lactones en route to Altohyrtin A
  作者：Stephen A. Hermitage、Alison Murphy、Stanley M. Roberts

  DOI：10.1016/s0960-894x(98)00268-6

  日期：1998.7

  Lactones 2 and 7 were synthesised and tested against six human tumour cell lines (Pancrens-a, BXPC-3), (Thyroid ca, KAT-4), (Thyroid ca, SW1736), (Lung-NSC, NCI-H460), (Pharynx-sq, FADU) and (Prostate, DU-145). Lactone 7 proved inactive, but lactone 2 displayed some activity against four of the six cell lines examined. Both lactones were converted into an intermediate 5 en route to Altohyrtin A. (C) 1998 Elsevier Science Ltd. All rights reserved.