(Z)-(R,S)-1-<(tert-Butyldimethylsilyl)oxy>-3-(tri-n-butylstannyl)-1-tridecene

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (Z)-(R,S)-1-<(tert-Butyldimethylsilyl)oxy>-3-(tri-n-butylstannyl)-1-tridecene
• 英文别名: tert-butyl-dimethyl-[(Z,3S)-3-tributylstannyltridec-1-enoxy]silane
• 化学式: C₃₁H₆₆OSiSn
• 分子量: 601.66
• InChiKey: BLKFPTOEQSJISF-BCUUCPOWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.27
• 重原子数：
  34
• 可旋转键数：
  23
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-氯丙醛 、 (Z)-(R,S)-1-<(tert-Butyldimethylsilyl)oxy>-3-(tri-n-butylstannyl)-1-tridecene 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 生成 (E,3R,4R)-4-[tert-butyl(dimethyl)silyl]oxy-1-chlorohexadec-5-en-3-ol 、
  参考文献：
  名称：

  Enantioselective Synthesis of (+)- and (-)-Muricatacin through SE2' Addition of Nonracemic .gamma.-Silyloxy Allylic Stannanes to Aldehydes

  摘要：

  The acetogenins (R,R)-(+)- and (S,S)-(-)-muricatacin were synthesized through the highly stereoselective addition of gamma-silyloxy allylic stannanes (S)-6 and (R)-6 to (E)-ethyl 8-formylpropenoate (12) in the presence of BF3.OEt(2). The resulting adducts (R,R)-13 and (S,S)-13 afforded the aforementioned acetogenins upon catalytic hydrogenation and subsequent deprotection-lactonization with aqueous HF. Interestingly, additions of stannanes 6 (racemic) to the saturated aldehydes RCH(2)CH(2)CHO (8, R = CO(2)Et, R = CN, R = Cl) in the presence of BF3.OEt(2) afforded ca. 70:30 mixtures of syn and anti adducts 9a-c. In contrast, the n-alkyl aldehyde 8 (R = n-C4H9) underwent highly selective syn addition (97:3) with the crotyl analogue 7 of stannane 6.

  DOI：

  10.1021/jo00094a023

文献信息

• Enantioselective Synthesis of (+)- and (-)-Muricatacin through SE2' Addition of Nonracemic .gamma.-Silyloxy Allylic Stannanes to Aldehydes
  作者：James A. Marshall、Gregory S. Welmaker

  DOI：10.1021/jo00094a023

  日期：1994.7

  The acetogenins (R,R)-(+)- and (S,S)-(-)-muricatacin were synthesized through the highly stereoselective addition of gamma-silyloxy allylic stannanes (S)-6 and (R)-6 to (E)-ethyl 8-formylpropenoate (12) in the presence of BF3.OEt(2). The resulting adducts (R,R)-13 and (S,S)-13 afforded the aforementioned acetogenins upon catalytic hydrogenation and subsequent deprotection-lactonization with aqueous HF. Interestingly, additions of stannanes 6 (racemic) to the saturated aldehydes RCH(2)CH(2)CHO (8, R = CO(2)Et, R = CN, R = Cl) in the presence of BF3.OEt(2) afforded ca. 70:30 mixtures of syn and anti adducts 9a-c. In contrast, the n-alkyl aldehyde 8 (R = n-C4H9) underwent highly selective syn addition (97:3) with the crotyl analogue 7 of stannane 6.