(1Z,4'S)-3-<(tert-Butyldiphenylsilyl)oxy>-1-(2',2'-dimethyl-1',3'-dioxolan-4'-yl)-1-propene | 154001-53-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1Z,4'S)-3-<(tert-Butyldiphenylsilyl)oxy>-1-(2',2'-dimethyl-1',3'-dioxolan-4'-yl)-1-propene
• 英文别名: (4S)-(Z)-1-(tert-Butyldiphenylsilyloxy)-4,5-isopropylidenedioxypent-2-ene；(1Z,4'S)-3-[(tert-Butyldiphenylsilyl)oxy]-1-(2',2'-dimethyl-1',3'-dioxolan-4'-yl)-1-propene；tert-butyl-[(Z)-3-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]prop-2-enoxy]-diphenylsilane
• CAS: 154001-53-3
• 化学式: C₂₄H₃₂O₃Si
• 分子量: 396.602
• InChiKey: WLDKWOPSIIGROC-CBUFDYBVSA-N

物化性质

• 沸点：
  445.6±45.0 °C(Predicted)
• 密度：
  1.05±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.27
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 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：

  (1Z,4'S)-3-<(tert-Butyldiphenylsilyl)oxy>-1-(2',2'-dimethyl-1',3'-dioxolan-4'-yl)-1-propene 在 盐酸 、 四氧化锇 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 吡啶 、 甲醇 为溶剂， 生成 Adonitol
  参考文献：
  名称：

  关于四氧化的立体化学氧化烯丙醇体系。经验法则

  摘要：

  提出了一种经验公式来预测烯丙基醇及其衍生物的主要渗透作用产物的立体化学。

  DOI：

  10.1016/0040-4020(84)80008-3
• 作为产物：
  描述：

  (R)-(+)-2,2-二甲基-1,3-二氧戊环-4-甲醛 在 咪唑 、 二异丁基氢化铝 作用下， 以 甲醇 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 2.5h， 生成 (1Z,4'S)-3-<(tert-Butyldiphenylsilyl)oxy>-1-(2',2'-dimethyl-1',3'-dioxolan-4'-yl)-1-propene
  参考文献：
  名称：

  Asymmetric Synthesis of (1'S,2'R)-Cyclopropyl Carbocyclic Nucleosides

  摘要：

  Enantiomeric synthesis of cyclopropyl carbocyclic nucleosides has been accomplished. The key intermediates 7 and 9 were synthesized from D-glyceraldehyde acetonide 1, which was converted to the alpha,beta-unsaturated ester 2 and then reduced to give allylic alcohol 3a. Stereoselective construction of the cyclopropyl ring of 3a and 3b followed by oxidation gave acid 5, which was treated under Curtius rearrangement conditions to obtain the urea intermediate 7. The urea intermediate was utilized to prepare uracil 14, thymine 15, and cytosine 18 nucleosides. The purine derivatives were prepared from cyclopropylamine 9 by condensation with 4,6-dichloro-5-form-amidopyrimidine or 4,6-dichloro-2-aminopyrimidine.

  DOI：

  10.1021/jo00121a047

文献信息

• Synthesis of analogues of the marine anti-tumour agent curacin A
  作者：Barbara K. D. Martin、John Mann、Olivia A. Sageot

  DOI：10.1039/a904378k

  日期：——

  A concise, multigram synthesis of (4R)-2-[(1′R,2′S)-1′,2′-methano-3′-(tert-butyldiphenylsiloxy)propyl]-4-hydroxymethyl-4,5-dihydrothiazole has been achieved, and this compound has been used for the production of a range of analogues of the anti-mitotic agent curacin A.

  实现了(4R)-2-[(1′R,2′S)-1′,2′-甲桥-3′-(叔丁基二苯基硅氧基)丙基]-4-羟甲基-4,5-二氢噻唑的简易多克合成，该化合物已被用于生产一系列抗有丝分裂剂仓霉素 A 的类似物。
• Synthesis of optically active cis- and trans-1,2-disubstituted cyclopropane derivatives by the Simmons-Smith reaction of allyl alcohol derivatives derived from (R)-2,3-O-isopropylideneglyceraldehyde
  作者：Tsutomu Morikawa、Hirofumi Sasaki、Ryo Hanai、Akira Shibuya、Takeo Taguchi

  DOI：10.1021/jo00080a017

  日期：1994.1

  The Simmons-Smith reactions of Z- and E-allyl alcohol derivatives 6 derived from (R)-2,3-O-isopropylideneglyceraldehyde (5) were used for the synthesis of optically active cis- and trans-1,2 disubstituted cyclopropane derivatives. Reaction of 6 with diethyl zinc and diiodomethane gave cyclopropane derivatives 7 in 84% to quantitative yields with 35 to approximate to 100% des. Identical facial selectivities toward the double bonds, Ire-asi for Z-6 and 1re-2re for E-6, were observed in the cyclopropanations. The diastereoselectivity was dependent on the protecting group on the terminal allylic oxygen (R of 6, TBDPS > MOM > Bn) and on the stereochemistry of the double bond (Z > E). For TBDPS ethers Z- and E-6c, cis- and trans-7c were obtained as single diastereomers respectively. It was clearly demonstrated that the stereoselectivity of the cyclopropanation is controlled by the directing effect of the allylic oxygen (O-1) of the dioxolane ring which coordinates to the reagent. The terminal allylic oxygen (O-2) lowered the diastereoselectivity This reaction was applied to the synthesis of optically active cyclopropane analogs of gamma-aminobutyric acid (GABA) 18, 22, and ent-22.
• Stereocontrolled synthesis of D-pentitols, 2-amino-2-deoxy-D-pentitols and 2-deoxy-D-pentitols from D-glyceraldehyde acetonide
  作者：Norio Minami、Soo Sung Ko、Yoshito Kishi

  DOI：10.1021/ja00368a040

  日期：1982.2
• On stereochemistry of osmium tetraoxide oxidation of allylic alcohol systems. Empirical rule
  作者：J.K. Cha、W.J. Christ、Y. Kishi

  DOI：10.1016/0040-4020(84)80008-3

  日期：1984.1

  An empirical formulation is presented to predict the stereochemistry of major osmylation products of allylic alcohols and their derivatives.

  提出了一种经验公式来预测烯丙基醇及其衍生物的主要渗透作用产物的立体化学。
• Asymmetric Synthesis of (1'S,2'R)-Cyclopropyl Carbocyclic Nucleosides
  作者：Yufen Zhao、Tefang Yang、Migyoung Lee、Doowon Lee、M. Gary Newton、Chung K. Chu

  DOI：10.1021/jo00121a047

  日期：1995.8

  Enantiomeric synthesis of cyclopropyl carbocyclic nucleosides has been accomplished. The key intermediates 7 and 9 were synthesized from D-glyceraldehyde acetonide 1, which was converted to the alpha,beta-unsaturated ester 2 and then reduced to give allylic alcohol 3a. Stereoselective construction of the cyclopropyl ring of 3a and 3b followed by oxidation gave acid 5, which was treated under Curtius rearrangement conditions to obtain the urea intermediate 7. The urea intermediate was utilized to prepare uracil 14, thymine 15, and cytosine 18 nucleosides. The purine derivatives were prepared from cyclopropylamine 9 by condensation with 4,6-dichloro-5-form-amidopyrimidine or 4,6-dichloro-2-aminopyrimidine.