(2R,4S,5R)-4-<2-(tert-butyldimethylsiloxy)ethyl>-2-phenyl-m-dioxan-5-ol | 217819-89-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶烷
• 英文名称: (2R,4S,5R)-4-<2-(tert-butyldimethylsiloxy)ethyl>-2-phenyl-m-dioxan-5-ol
• 英文别名: 3,5-O-Benzylidene-1-O-[tert-butyl(dimethyl)silyl]-2-deoxy-D-erythro-pentitol；(2R,4S,5R)-4-[2-[tert-butyl(dimethyl)silyl]oxyethyl]-2-phenyl-1,3-dioxan-5-ol
• CAS: 217819-89-1
• 化学式: C₁₈H₃₀O₄Si
• 分子量: 338.519
• InChiKey: BQBVBMQHKPFTBP-IXDOHACOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.87
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  47.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2R,4S,5R)-4-<2-(tert-butyldimethylsiloxy)ethyl>-2-phenyl-m-dioxan-5-ol 在 Oxone 、 正丁基锂 、 cerium(III) chloride 、 草酰氯 、 18-冠醚-6 、 四丁基氟化铵 、 叔丁基锂 、 氧气 、 四丁基碘化铵 、 potassium hydride 、 双(三甲基硅烷基)氨基钾 、 碳酸氢钠 、 戴斯-马丁氧化剂 、 氟化氢吡啶 、 二甲基亚砜 、 三乙胺 、 N,N-二异丙基乙胺 、 三苯基膦 、 红铝 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 、 乙腈 为溶剂， 反应 8.25h， 生成 (2R,4S,5S)-5-(benzyloxy)-4-<(1E,3S,4R,7R,8S)-7-(methoxymethoxy)-4,11,11-trimethyl-5,6-dioxobicyclo-<6.2.1>undec-1-en-3-yl>-2-phenyl-m-dioxane-4-acetaldehyde
  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：

  (2R,4S,5R)-5-hydroxy-2-phenyl-4-vinyl-1,3-dioxane 在 咪唑 、 sodium hydroxide 、 9-borabicyclo[3.3.1]nonane dimer 、 双氧水 作用下， 以 二氯甲烷 为溶剂， 生成 (2R,4S,5R)-4-<2-(tert-butyldimethylsiloxy)ethyl>-2-phenyl-m-dioxan-5-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

• Intramolecular addition of acyl radicals to α-substituted vinylogous carbonates: demonstrating the effect of ring size on acyclic stereocontrolElectronic supplementary information (ESI) available: spectral data (IR, 1H and 13C NMR) and high resolution MS for 1/2a-c, 7–10. See http://www.rsc.org/suppdata/cc/b1/b106766b/
  作者：P. Andrew Evans、Sushil Raina、Khalid Ahsan

  DOI：10.1039/b106766b

  日期：2001.11.22

  The level of stereocontrol obtained in the reduction of the free radical derived from the intramolecular addition of an acyl radical to an α-branched vinylogous carbonate is dependent upon the ring-size of the cyclic ether.

  从一个酸基自由基向α-支链的乙烯基碳酸酯的分子内加成所获得的自由基还原反应中的立体控制水平，依赖于环醚的环大小。
• Stereochemical Models for the Enantiocontrolled Construction of Fully Functionalized C Rings via Intramolecular Aldolization in Advanced Precursors to Paclitaxel
  作者：Leo A. Paquette、Qingbei Zeng、Hon-Chung Tsui、Jeffrey N. Johnston

  DOI：10.1021/jo981749j

  日期：1998.11.1

  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.