(2R,3R)-(-)-2,3-dimethyl-1,4-dioxaspiro<4.4>non-6-ene-6-methanol | 135040-91-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R,3R)-(-)-2,3-dimethyl-1,4-dioxaspiro<4.4>non-6-ene-6-methanol
• 英文别名: [(2R,3R)-2,3-dimethyl-1,4-dioxaspiro[4.4]non-8-en-9-yl]methanol
• CAS: 135040-91-4
• 化学式: C₁₀H₁₆O₃
• 分子量: 184.235
• InChiKey: JLVLJCJMQFXDES-HTQZYQBOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.22
• 重原子数：
  13.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  38.69
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (2R,3R)-(-)-2,3-dimethyl-1,4-dioxaspiro<4.4>non-6-ene-6-methanol 在 咪唑 、 叔丁基过氧化氢 、 三氢化钐 、 lithium aluminium tetrahydride 、 正丁基锂 、 selenium(IV) oxide 、 草酰氯 、 potassium tert-butylate 、 sodium methylate 、 对甲苯磺酸 、 二甲基亚砜 、 三乙胺 、 mercury dichloride 作用下， 以 四氢呋喃 、 甲醇 、 异辛烷 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 65.42h， 生成 <1R-<1α(R*),3aβ,4α<(E)-(1S*,3S*,5R*)>,7aα>>-1-<1,5-dimethyl-5-<(trimethylsilyl)oxy>hexyl>-4-<2-<3-<<(1,1-dimethylethyl)diphenylsilyl>oxy>-2-methylenebicyclo<3.1.0>hexan-1-yl>ethenyl>octahydro-7a-methyl-1H-inden-4-ol
  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：

  (2R,3R)-(-)-2,3-丁二醇 、 2-羟基甲基-2-环戊酮 在 4-甲基苯磺酸吡啶 作用下， 以68%的产率得到(2R,3R)-(-)-2,3-dimethyl-1,4-dioxaspiro<4.4>non-6-ene-6-methanol
  参考文献：
  名称：

  Control of stereoselectivity in samarium metal induced cyclopropanations. Synthesis of 1,25-dihydroxycholecalciferol

  摘要：

  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.

  DOI：

  10.1016/s0040-4039(00)79919-9

文献信息

• Catalytic Antibodies in Synthesis:  Design and Synthesis of a Hapten for Application to the Preparation of a Scalemic Pyrrolidine Ring Synthon for Ptilomycalin A
  作者：Glen T. Anderson、Michael D. Alexander、Scott D. Taylor、David B. Smithrud、Stephen J. Benkovic、Steven M. Weinreb

  DOI：10.1021/jo951469t

  日期：1996.1.1

  A catalytic antibody-based approach toward the synthesis of an optically active pyrrolidine ring synthon potentially useful for ptilomycalin A is described. Enantiomerically pure hapten 37 was designed and constructed with the eventual goal of generating antibodies for the enantioselective partial hydrolysis of a meso diester such as 44 into a monoacid 45. This transition state analog possesses a phosphonate group containing the requisite oxyanionic character of the tetrahedral intermediate for ester hydrolysis. A newly developed carbamate-based linker, which was found to be much more hydrolytically stable than the commonly used glutarate ester, was developed for coupling of the hapten to a carrier protein.
• 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.