(2R,3S)-2,3-bis(benzyloxy)-4-(tert-butyldiphenylsilyloxy)butanal | 1217463-62-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2R,3S)-2,3-bis(benzyloxy)-4-(tert-butyldiphenylsilyloxy)butanal
• 英文别名: (2R,3S)-2,3-Bis(benzyloxy)-4-{[tert-butyl(diphenyl)silyl]oxy}butanal；(2R,3S)-4-[tert-butyl(diphenyl)silyl]oxy-2,3-bis(phenylmethoxy)butanal
• CAS: 1217463-62-1
• 化学式: C₃₄H₃₈O₄Si
• 分子量: 538.759
• InChiKey: LAFGBUQFASSPSN-LQJZCPKCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.93
• 重原子数：
  39
• 可旋转键数：
  14
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2R,3S)-2,3-bis(benzyloxy)-4-(tert-butyldiphenylsilyloxy)butanal 在 mercury(II) diacetate 、 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 21.0h， 生成 (5S,6S)-5,6-bis(benzyloxy)-7-[(tert-butyldiphenylsilyl)oxy]-2-methylhept-1-en-3-ol
  参考文献：
  名称：

  A Stereoconvergent Intramolecular Diels–Alder Cycloaddition Related to the Construction of the Decalin Core of neo-Clerodane Diterpenoids

  摘要：

  Several examples of a highly specific, stereoconvergent intramolecular Diels-Alder cycloaddition that led to the trans-decalin core of neo-clerodane diterpenoids are described. The relative configuration adjacent to the dienophile, which led to C4 of the decalin system, as well as the electron withdrawing effects of various substituents and conformational rigidity of the Diels-Alder precursors were explored.

  DOI：

  10.1021/jo400029u
• 作为产物：
  描述：

  1,4-di-O-benzyl-L-threitol 在 草酰氯 、 sodium hydride 作用下， 以 四氢呋喃 、 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 5.0h， 生成 (2R,3S)-2,3-bis(benzyloxy)-4-(tert-butyldiphenylsilyloxy)butanal
  参考文献：
  名称：

  Investigation of Diastereoselective Acyclic α-Alkoxydithioacetal Substitutions Involving Thiacarbenium Intermediates

  摘要：

  Reported herein is an experimental and theoretical study that elucidates why silylated nucleobase additions to acyclic alpha-alkoxythiacarbenium intermediates proceed with high 1,2-syn stereocontrol (anti-Felkin-Anh), which is opposite to what would be expected with corresponding activated aldehydes. The acyclic thioaminals formed undergo intramolecular cyclizations to provide nucleoside analogues with anticancer and antiviral properties. The factors influencing the selectivity of the substitution reaction have been examined thoroughly. Halothioether species initially form, ionize in the presence (low dielectric media) or absence (higher dielectric media) of the nucleophile, and react through S(N)2-like transition structures (TS A and D), where the a-alkoxy group is gauche to the thioether moiety. An important, and perhaps counterintuitive, observation in this work was that calculations done in the gas phase or low dielectric media (toluene) are essential to locate the product- and rate-determining transition structures (C-N bond formation) that allow the most reasonable prediction of selectivity and isotope effects for more polar solvents (THF, MeCN). The triangle triangle G +/- (G(TSA)-(TSD)) obtained in silico are consistent with the preferential formation of 1,2-syn product and with the trends of stereocontrol displayed by 2,3-anti and 2,3-syn alpha,beta-bis-alkoxydithioacetals.

  DOI：

  10.1021/jo502181a

文献信息

• Investigation of Diastereoselective Acyclic α-Alkoxydithioacetal Substitutions Involving Thiacarbenium Intermediates
  作者：Michel Prévost、Starr Dostie、Marie-Ève Waltz、Yvan Guindon

  DOI：10.1021/jo502181a

  日期：2014.11.7

  Reported herein is an experimental and theoretical study that elucidates why silylated nucleobase additions to acyclic alpha-alkoxythiacarbenium intermediates proceed with high 1,2-syn stereocontrol (anti-Felkin-Anh), which is opposite to what would be expected with corresponding activated aldehydes. The acyclic thioaminals formed undergo intramolecular cyclizations to provide nucleoside analogues with anticancer and antiviral properties. The factors influencing the selectivity of the substitution reaction have been examined thoroughly. Halothioether species initially form, ionize in the presence (low dielectric media) or absence (higher dielectric media) of the nucleophile, and react through S(N)2-like transition structures (TS A and D), where the a-alkoxy group is gauche to the thioether moiety. An important, and perhaps counterintuitive, observation in this work was that calculations done in the gas phase or low dielectric media (toluene) are essential to locate the product- and rate-determining transition structures (C-N bond formation) that allow the most reasonable prediction of selectivity and isotope effects for more polar solvents (THF, MeCN). The triangle triangle G +/- (G(TSA)-(TSD)) obtained in silico are consistent with the preferential formation of 1,2-syn product and with the trends of stereocontrol displayed by 2,3-anti and 2,3-syn alpha,beta-bis-alkoxydithioacetals.
• A Stereoconvergent Intramolecular Diels–Alder Cycloaddition Related to the Construction of the Decalin Core of <i>neo</i>-Clerodane Diterpenoids
  作者：Sean C. Butler、Craig J. Forsyth

  DOI：10.1021/jo400029u

  日期：2013.4.19

  Several examples of a highly specific, stereoconvergent intramolecular Diels-Alder cycloaddition that led to the trans-decalin core of neo-clerodane diterpenoids are described. The relative configuration adjacent to the dienophile, which led to C4 of the decalin system, as well as the electron withdrawing effects of various substituents and conformational rigidity of the Diels-Alder precursors were explored.