(1S-cis)-1-ethynylbicyclo<3.1.0>hexan-2-one | 135040-95-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S-cis)-1-ethynylbicyclo<3.1.0>hexan-2-one
• 英文别名: (1S,5R)-1-ethynylbicyclo[3.1.0]hexan-2-one
• CAS: 135040-95-8
• 化学式: C₈H₈O
• 分子量: 120.151
• InChiKey: WBUDMQMEVZKYHS-SVRRBLITSA-N

物化性质

• 沸点：
  173.0±19.0 °C(Predicted)
• 密度：
  1.12±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1S-cis)-1-ethynylbicyclo<3.1.0>hexan-2-one 在 咪唑 、 叔丁基过氧化氢 、 lithium aluminium tetrahydride 、 正丁基锂 、 selenium(IV) oxide 、 甲基叔丁基醚 、 乙酸9-蒽基酯 、 potassium tert-butylate 、 四丁基氟化铵 、 sodium methylate 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 甲醇 、 异辛烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 34.33h， 生成 骨化三醇
  参考文献：
  名称：

  Convergent Synthesis of Vitamin D₃ Metabolites. Control of the Stereoselectivity in Samarium-Induced Cyclopropanations of Cyclopentenes

  摘要：

  The 25-hydroxy and 1 alpha,25-dihydroxy vitamin D-3 metabolites are obtained by solvolytic rearrangements of the 1-desoxy and 1 alpha-hydroxy cyclopropyl vinylogous alcohols 31 and 29, respectively, with simultaneous formation of the vitamin D structural triene and the 3-hydroxy function. Two complementary methods have been employed to direct the stereoselectivity ofthe samarium induced olefin cyclopropanations which ultimately lead to key chiral ring A precursors. One protocol uses the two stereogenic centers of the (R,R)-B,S-butanediol ketal moiety of 8, while the other method uses the allylic hydroxyl group of(R)-16.

  DOI：

  10.1021/jo951229d
• 作为产物：
  描述：

  2-羟基甲基-2-环戊酮 在 三氢化钐 、 草酰氯 、 potassium tert-butylate 、 4-甲基苯磺酸吡啶 、 对甲苯磺酸 、 二甲基亚砜 、 三乙胺 、 mercury dichloride 作用下， 以 四氢呋喃 、 四氯化碳 、 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 60.08h， 生成 (1S-cis)-1-ethynylbicyclo<3.1.0>hexan-2-one
  参考文献：
  名称：

  Convergent Synthesis of Vitamin D₃ Metabolites. Control of the Stereoselectivity in Samarium-Induced Cyclopropanations of Cyclopentenes

  摘要：

  The 25-hydroxy and 1 alpha,25-dihydroxy vitamin D-3 metabolites are obtained by solvolytic rearrangements of the 1-desoxy and 1 alpha-hydroxy cyclopropyl vinylogous alcohols 31 and 29, respectively, with simultaneous formation of the vitamin D structural triene and the 3-hydroxy function. Two complementary methods have been employed to direct the stereoselectivity ofthe samarium induced olefin cyclopropanations which ultimately lead to key chiral ring A precursors. One protocol uses the two stereogenic centers of the (R,R)-B,S-butanediol ketal moiety of 8, while the other method uses the allylic hydroxyl group of(R)-16.

  DOI：

  10.1021/jo951229d

文献信息

• Control of stereoselectivity in samarium metal induced cyclopropanations. Synthesis of 1,25-dihydroxycholecalciferol
  作者：M. Kabat、J. Kiegiel、N. Cohen、K. Toth、P.M. Wovkulich、M.R. Uskoković

  DOI：10.1016/s0040-4039(00)79919-9

  日期：1991.5

  1,25-Dihydroxycholecalciferol (23) was synthesized from A-ring precursor 18 and Windaus-Grundmann ketone 19 via cyclovitamin D 21. Key reactions include highly stereoselective (5 to 6) and stereospecific (13 to 14) cyclopropanations.
• Convergent Synthesis of Vitamin D₃ Metabolites. Control of the Stereoselectivity in Samarium-Induced Cyclopropanations of Cyclopentenes
  作者：M. M. Kabat、J. Kiegiel、N. Cohen、K. Toth、P. M. Wovkulich、M. R. Uskoković

  DOI：10.1021/jo951229d

  日期：1996.1.1

  The 25-hydroxy and 1 alpha,25-dihydroxy vitamin D-3 metabolites are obtained by solvolytic rearrangements of the 1-desoxy and 1 alpha-hydroxy cyclopropyl vinylogous alcohols 31 and 29, respectively, with simultaneous formation of the vitamin D structural triene and the 3-hydroxy function. Two complementary methods have been employed to direct the stereoselectivity ofthe samarium induced olefin cyclopropanations which ultimately lead to key chiral ring A precursors. One protocol uses the two stereogenic centers of the (R,R)-B,S-butanediol ketal moiety of 8, while the other method uses the allylic hydroxyl group of(R)-16.