(1S,2S,3R,4S)-1-<(E)-2-<(2R,4S,5S)-5-(benzyloxy)-4-<2-(tert-butyldimethylsiloxy)ethyl>-2-phenyl-m-dioxan-5-yl>vinyl>-3-(methoxymethoxy)-7,7-dimethyl-2-<(E)-1-propenyl>bicyclo<2.2.1>heptan-2-ol | 217820-03-6

• 分子结构分类: 有机化合物
• 英文名称: (1S,2S,3R,4S)-1-<(E)-2-<(2R,4S,5S)-5-(benzyloxy)-4-<2-(tert-butyldimethylsiloxy)ethyl>-2-phenyl-m-dioxan-5-yl>vinyl>-3-(methoxymethoxy)-7,7-dimethyl-2-<(E)-1-propenyl>bicyclo<2.2.1>heptan-2-ol
• 英文别名: (1S,2S,3R,4S)-1-[(E)-2-[(2R,4S,5S)-4-[2-[tert-butyl(dimethyl)silyl]oxyethyl]-2-phenyl-5-phenylmethoxy-1,3-dioxan-5-yl]ethenyl]-3-(methoxymethoxy)-7,7-dimethyl-2-[(E)-prop-1-enyl]bicyclo[2.2.1]heptan-2-ol
• CAS: 217820-03-6
• 化学式: C₄₁H₆₀O₇Si
• 分子量: 693.009
• InChiKey: MJYVUNSDGXBQPB-AXVBYICCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.76
• 重原子数：
  49
• 可旋转键数：
  15
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  75.6
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (1S,2S,3R,4S)-1-<(E)-2-<(2R,4S,5S)-5-(benzyloxy)-4-<2-(tert-butyldimethylsiloxy)ethyl>-2-phenyl-m-dioxan-5-yl>vinyl>-3-(methoxymethoxy)-7,7-dimethyl-2-<(E)-1-propenyl>bicyclo<2.2.1>heptan-2-ol 在 18-冠醚-6 、 氧气 、 双(三甲基硅烷基)氨基钾 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 以72%的产率得到(1S,2R,5R,6S,7E)-6-<(2R,4S,5S)-5-(benzyloxy)-4-<2-(tert-butyldimethylsiloxy)ethyl>-2-phenyl-m-dioxan-5-yl>-4-hydroxy-2-(methoxymethoxy)-5,11,11-trimethylbicyclo<6.2.1>undec-7-en-3-one
  参考文献：
  名称：

  Stereochemical Models for the Enantiocontrolled Construction of Fully Functionalized C Rings via Intramolecular Aldolization in Advanced Precursors to Paclitaxel

  摘要：

  Six transition-state models for intramolecular aldol C-ring annulation in suitably substituted bicyclo-[6.2.1]undecanones have been defined. The first consideration is the inherent conformational flexibility of the nine-membered ketonic ring which does not limit effective deprotonation to a single C-8 epimer. When the oxygen substituents at C-4 and C-5 are not covalently linked, the configuration at C-5 defines the stereochemical course of the ring closure, with only the beta series being amenable to the proper elaboration of paclitaxel. When C-4 and C-5 are incorporated into a 1,3-dioxane ring instead, the principal stereocontrol element is translocated into the aryl-substituted carbon of the cyclic acetal. To the extent that the Ar group remains equatorially disposed, then proper aldolization will materialize in only one of the four possible diastereomers. Experimental tests that are provided for three of the models are shown to conform to expectations. This analysis of the origin of stereoselectivity has, for the first time, defined the scope and limitations associated with C-ring closure by means of the aldol protocol.

  DOI：

  10.1021/jo981749j
• 作为产物：
  描述：

  (1S,4R)-1-(2,2-dibromovinyl)-7,7-dimethylbicyclo<2.2.1>heptan-2-one 在 Oxone 、 sodium tetrahydroborate 、 正丁基锂 、 cerium(III) chloride 、 18-冠醚-6 、 四丁基氟化铵 、 叔丁基锂 、 四丁基碘化铵 、 potassium hydride 、 碳酸氢钠 、 戴斯-马丁氧化剂 、 N,N-二异丙基乙胺 、 红铝 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 甲苯 为溶剂， 反应 6.0h， 生成 (1S,2S,3R,4S)-1-<(E)-2-<(2R,4S,5S)-5-(benzyloxy)-4-<2-(tert-butyldimethylsiloxy)ethyl>-2-phenyl-m-dioxan-5-yl>vinyl>-3-(methoxymethoxy)-7,7-dimethyl-2-<(E)-1-propenyl>bicyclo<2.2.1>heptan-2-ol
  参考文献：
  名称：

  Stereochemical Models for the Enantiocontrolled Construction of Fully Functionalized C Rings via Intramolecular Aldolization in Advanced Precursors to Paclitaxel

  摘要：

  Six transition-state models for intramolecular aldol C-ring annulation in suitably substituted bicyclo-[6.2.1]undecanones have been defined. The first consideration is the inherent conformational flexibility of the nine-membered ketonic ring which does not limit effective deprotonation to a single C-8 epimer. When the oxygen substituents at C-4 and C-5 are not covalently linked, the configuration at C-5 defines the stereochemical course of the ring closure, with only the beta series being amenable to the proper elaboration of paclitaxel. When C-4 and C-5 are incorporated into a 1,3-dioxane ring instead, the principal stereocontrol element is translocated into the aryl-substituted carbon of the cyclic acetal. To the extent that the Ar group remains equatorially disposed, then proper aldolization will materialize in only one of the four possible diastereomers. Experimental tests that are provided for three of the models are shown to conform to expectations. This analysis of the origin of stereoselectivity has, for the first time, defined the scope and limitations associated with C-ring closure by means of the aldol protocol.

  DOI：

  10.1021/jo981749j

文献信息

• Reversible Charge-Accelerated Oxy-Cope Rearrangements
  作者：Hon-Chung Tsui、Leo A. Paquette

  DOI：10.1021/jo982002w

  日期：1998.12.1

  An asymmetric synthesis of the oxetane-containing norbornanone 23 and its coupling to trans-1-propenyllithium to give 24 are reported, in tandem with the preparation of the related alcohols 28 and 30. All three divinyl carbinols undergo anionic oxy-Cope rearrangement very rapidly at low temperature. Quenching of 24(-)K(+) and 28(-)K(+) under these conditions with water or various aqueous salt solutions results in protonation of the alkoxides. If these reaction mixtures are poured instead onto cold (0 degrees C) silica gel, their sigmatropically related ketones are isolated in very good yield. Whereas the 24(-)K(+) <--(-->) 25(-)K(+) equilibrium pair is not reactive to molecular oxygen, 30(-)K(+) is directly converted into an a-hydroperoxy ketone under comparable conditions. These and additional observations are rationalized in the context of atropisomerism involving conversion of oxygen-up enolates, formed reversibly under kinetically controlled conditions, into their thermodynamically favored, more reactive oxygen-down conformers.