cis-(1R,4S)-4-tert-butyldimethylsilyloxymethyl-2-cyclopenten-1-ol | 201340-81-0

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: cis-(1R,4S)-4-tert-butyldimethylsilyloxymethyl-2-cyclopenten-1-ol
• 英文别名: (1R,4S)-(+)-4-(tert-Butyldimethylsiloxymethyl)cyclopent-2-enol；(1R,4S)-4-[[tert-butyl(dimethyl)silyl]oxymethyl]cyclopent-2-en-1-ol
• CAS: 201340-81-0
• 化学式: C₁₂H₂₄O₂Si
• 分子量: 228.407
• InChiKey: REQFKGQMIDQOOU-MNOVXSKESA-N

物化性质

• 沸点：
  265.3±23.0 °C(Predicted)
• 密度：
  0.946±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.95
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  cis-(1R,4S)-4-tert-butyldimethylsilyloxymethyl-2-cyclopenten-1-ol 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以83%的产率得到顺式-4-羟基-2-环戊烯-1-甲醇
  参考文献：
  名称：

  Alkoxy group facilitated ring closing metathesis (RCM) of acyclic 1,6-dienes. Convenient synthesis of non-racemic highly substituted cyclopentenols

  摘要：

  Alkoxymethyl groups at the C-5 allylic position of 1,6-dienols have been found to accelerate RCM reactions significantly with the Grubbs' catalyst PhCH=Ru(PCY3)(2)Cl-2. This phenomenon has been used for direct access to highly substituted cyclopentenols, potential intermediates in the synthesis of carbovir, abacavir and BCA. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2004.06.127
• 作为产物：
  描述：

  cis-(+/-)-1,2-epoxy-4-(hydroxymethyl)cyclopentane 在 咪唑 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 Lithium (S)-2-(1-pyrrolidinylmethyl)pyrrolidide 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 48.0h， 生成 cis-(1R,4S)-4-tert-butyldimethylsilyloxymethyl-2-cyclopenten-1-ol
  参考文献：
  名称：

  An asymmetric synthesis of (−)-carbovir

  摘要：

  Enantioselective deprotonation of trans-4-t-butyldimethylsiloxymethyl-1,2-epoxycyclopentane (trans-4) by a chiral lithium amide, lithium (S)-2-(pyrrolidin-1-ylmethyl)pyrrolidide (1), afforded (1S,4S)-trans-4-t-butyldimethylsiloxymethyl-2-cyclopenten-1-ol (trans-7) in 83 %ee. Alcohol trans-7 was easily transformed to (-)-carbovir, an anti-HIV carbocyclic nucleoside.

  DOI：

  10.1016/0957-4166(94)80072-3

文献信息

• A Concise Enantioselective Pathway to Carbocyclic Nucleoside: Asymmetric Synthesis of Carbocyclic Moiety of Carbovir
  作者：Shinji Tanimori、Masakazu Tsubota、Mingqi He、Mitsuru Nakayama

  DOI：10.1080/00397919708004098

  日期：1997.7

  Abstract (-)-Trans-4-t-butyldimethylsilyloxymethyl-2-cyclopentenol (13), a key intermediate for the synthesis of (-)-carbovir (15), was synthesized by using enantioselective bicyclic ring construction of chiral α-diazo-β-keto ester 3 catalyzed by rhodium (II) acetate.

  摘要 (-)-Trans-4-t-丁基二甲基甲硅烷氧基甲基-2-环戊烯醇 (13) 是合成 (-)-卡波韦 (15) 的关键中间体，通过使用手性 α-重氮基的对映选择性双环结构合成。由醋酸铑 (II) 催化的 β-酮酯 3。
• An Efficient Synthesis of Chiral Nonracemic Diamines: Application in Asymmetric Synthesis
  作者：Parthasarathy Saravanan、Vinod K Singh

  DOI：10.1016/s0040-4039(97)10578-0

  日期：1998.1

  A variety of chiral diamines have been synthesized from optically active mandelic acid in an efficient manner. The chiral nonracemic lithium amide base derived from one of the diamines has been used in formal asymmetric synthesis of natural products such as (−)-utenone A and (−)-carbovir. © 1997 Elsevier Science Ltd. All rights reserved.

  已经从旋光的扁桃酸中有效地合成了各种手性二胺。衍生自一种二胺的手性非外消旋锂酰胺碱已用于天然产物如（-）-泛酮A和（-）-carbovir的形式不对称合成。©1997 Elsevier ScienceLtd。保留所有权利。
• A New Nucleophilic Ring Opening of an Activated Cyclopropane and a Formal Synthesis of (±)-Carbovir
  作者：Shinji Tanimori、Masakazu Tsubota、Mingqi He、Mitsuru Nakayama

  DOI：10.1271/bbb.59.2091

  日期：1995.1

  The reaction of bicyclo[3.1.0]hexane 1, possessing a doubly activated cyclopropane ring, with acetic acid and potassium acetate in DMSO proceeded smoothly to give the adduct 2 in good yield. A formal total synthesis of the potent anti-HIV agent (+/-)-carbovir (9) was done by converting 2 into a known precursor 8 in 8 steps via allyl alcohol 7 including the regioselective introduction of a double bond

  具有双活化环丙烷环的双环[3.1.0]己烷1与乙酸和乙酸钾在DMSO中的反应顺利进行，从而以高收率得到加合物2。有效的抗HIV药物（+/-）-carbovir（9）的正式总合成是通过烯丙醇7分8步将2转化为已知的前体8进行的，包括区域选择性引入双键（4至5 ）和使用Mitsunobu反应（7至8）连接核碱基。
• Synthesis of chiral non-racemic 1,2-diamines from O-acetyl mandelic acid: application in enantioselective deprotonation of epoxides and diethylzinc addition to aldehydes
  作者：P Saravanan、Alakesh Bisai、S Baktharaman、M Chandrasekhar、Vinod K Singh

  DOI：10.1016/s0040-4020(02)00376-9

  日期：2002.6

  A variety of 1,2-diamines were synthesized from readily available O-acetyl mandelic acid. These diamines were used in the synthesis of key intermediates for the preparation of (-)-utenone A and carbovir involving enantioselective deprotonation of epoxides, The addition of Et2Zn catalysed by some of these diamines was also studied and although ees were not high, some interesting observations were made in the outcome of the stereochemistry of the product. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Synthesis of (±)-2′,3′-didehydro-2′,3′-dideoxy nucleosides via a modified Prins reaction and palladium(<scp>0</scp>) catalysed coupling
  作者：Elizabeth A. Saville-Stones、Stephen D. Lindell、Neil S. Jennings、John C. Head、Mark J. Ford

  DOI：10.1039/p19910002603

  日期：——

  Cyclopentenyl allylic acetates have been prepared in diastereoisomerically enriched form by modification of the Prins reaction. Palladium(o) catalysed coupling between these allylic acetates and a heteroaromatic base provides a highly convergent and direct route for synthesising carbocyclic 2',3'-didehydro-2',3'-dideoxy nucleosides. The method is exemplified by the coupling reaction with adenine which yields (+/-)-2',3'-didehydro-2',3'-dideoxyaristeromycin 5'-O-acetate 22 in 50% yield. This has been converted in two steps into (+/-)-aristeromycin triacetate 5.