硅烷,[[(1R,2R)-2-[(4S)-2,2-二甲基-1,3-二噁戊环-4-基]环丙基]甲氧基](1,1-二甲基乙基)二苯基- | 154001-57-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 硅烷,[[(1R,2R)-2-[(4S)-2,2-二甲基-1,3-二噁戊环-4-基]环丙基]甲氧基](1,1-二甲基乙基)二苯基-
• 英文名称: tert-butyl-[(1R,2R)-2-((S)-2,2-dimethyl[1,3]dioxolan-4-yl)cyclopropylmethyl]diphenylsilane
• 英文别名: tert-butyl-[[(1R,2R)-2-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]cyclopropyl]methoxy]-diphenylsilane
• CAS: 154001-57-7
• 化学式: C₂₅H₃₄O₃Si
• 分子量: 410.629
• InChiKey: YLFIHWKTVLRBOX-WWPVKYPJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.35
• 重原子数：
  29
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.52
• 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：

  硅烷,[[(1R,2R)-2-[(4S)-2,2-二甲基-1,3-二噁戊环-4-基]环丙基]甲氧基](1,1-二甲基乙基)二苯基- 在 Candia cylindracea lipase 四丁基氟化铵 、 2-碘酰基苯甲酸 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二甲基亚砜 为溶剂， 生成 [(1R)-1-[(1R,2R)-2-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]cyclopropyl]but-3-enyl] acetate
  参考文献：
  名称：

  关于苏糖内酯总合成的研究：环丙烷-内酯链段的立体选择性合成

  摘要：

  已经开发了一种简单的立体选择路线，以合成茄醛酸内酯的右手片段，在该方法中，首先合成关键的双功能环丙烷中间体2，然后以良好的总收率构建了八元内酯环。

  DOI：

  10.1016/s0040-4039(97)10731-6
• 作为产物：
  描述：

  (S)-4,5-异亚丙基-2-戊醇 在 咪唑 、 diethylzinc 作用下， 以 二氯甲烷 为溶剂， 生成 硅烷,[[(1R,2R)-2-[(4S)-2,2-二甲基-1,3-二噁戊环-4-基]环丙基]甲氧基](1,1-二甲基乙基)二苯基-
  参考文献：
  名称：

  关于苏糖内酯总合成的研究：环丙烷-内酯链段的立体选择性合成

  摘要：

  已经开发了一种简单的立体选择路线，以合成茄醛酸内酯的右手片段，在该方法中，首先合成关键的双功能环丙烷中间体2，然后以良好的总收率构建了八元内酯环。

  DOI：

  10.1016/s0040-4039(97)10731-6

文献信息

• Enantioselective Total Synthesis of (-)-Clavosolide A and B
  作者：Jung-Beom Son、Si-Nae Kim、Na-Yeong Kim、Min-Ho Hwang、Won-Sun Lee、Duck-Hyung Lee

  DOI：10.5012/bkcs.2010.31.03.653

  日期：2010.3.20

  Enantioselective total synthesis of (-)-clavosolide A and B was reported in full including the synthesis of proposed structure of (-)-clavosoldie A (1), revised structure of (-)-clavosoldie A (5), and revised structure of (-)-clavosoldie B (6). The relative and absolute stereochemistries of the natural products were confirmed unambiguously by comparing the optical rotation values and $^1H$ and $^13}C$ NMR spectra of them.

  完全报道了(-)-clavosolide A和B的对映选择性全合成，包括所提出的(-)-clavosolide A (1)结构的合成、修订后的(-)-clavosolide A (5)结构的合成以及修订后的(-)-clavosolide B (6)结构的合成。通过比较其旋光值和$^1H$及$^13}C$核磁共振谱，明确证实了这些天然产物的相对和绝对立体化学。
• The synthesis of single enantiomers of meromycolic acids from mycobacterial wax esters
  作者：Juma'a R. Al Dulayymi、Mark S. Baird、Evan Roberts、David E. Minnikin

  DOI：10.1016/j.tet.2006.09.019

  日期：2006.12

  Three stereoisomers of a wax ester meromycolate have been prepared starting from mannitol. A detailed comparison of their NMR spectra with those reported for a homologous series of natural wax esters allows the relative configurations of the α-methyl group and adjacent trans-cyclopropane to be determined.

  从甘露糖醇开始已经制备了蜡酯巯基甲酸酯的三种立体异构体。将它们的NMR光谱与天然蜡酯的同源系列报道的NMR光谱进行详细比较，可以确定α-甲基和相邻的反式-环丙烷的相对构型。
• Total syntheses of <i>ent</i>-hypocoprin A and <i>ent</i>-hypocoprin B
  作者：Koichiro Ota、Taiki Watanabe、Shuntaro Igarashi、Shinnosuke Okazaki、Kazuo Kamaike、Hiroaki Miyaoka

  DOI：10.1039/d2ra02891c

  日期：——

  bicyclic skeletal sesquiterpenoids, namely, hypocoprin A and hypocoprin B. The synthesis involved conjugate addition accelerated by trimethylsilyl chloride, construction of the ten-membered ring via the intramolecular SN2 reaction promoted by 1,8-diazabicyclo[5.4.0]undec-7-ene, and osmium-mediated π-facial selective dihydroxylation to functionalize the 1,1-disubstituted alkene.

  本研究报告了独特的 3/10 双环骨架倍半萜类化合物的对映体，即次菌素 A 和次菌素 B 的立体选择性全合成。合成涉及三甲基氯硅烷加速的共轭加成，通过分子内 S N构建十元环1,8-二氮杂双环[5.4.0]十一碳-7-烯促进的2反应，以及锇介导的π-面选择性二羟基化以官能化1,1-二取代烯烃。
• The first asymmetric total syntheses of 3((1R,2R)- and 3((1S,2R)-2-(12-methyltridecyl)cyclopropyl)propanoic acid
  作者：Debendra K. Mohapatra、Nagesh Guguloth、J.S. Yadav

  DOI：10.1016/j.tetlet.2012.09.133

  日期：2012.12

  The first efficient total syntheses of 3((1 R,2R)- and 3((1S,2R)-2-(12-methyltridecyl)cyclopropyl)propanoic acid have been achieved following a chelation controlled modified Simmon-Smith cyclopropanation, Wittig reaction, Horner-Wadsworth-Emmons olefination, and p-toluenesulfonyl hydrazide catalyzed hydrogenation as key reactions in good overall yield. (C) 2012 Elsevier Ltd. All rights reserved.
• 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.