(1S,2R)-2-tert-butyldiphenylsilyloxymethyl-1-[(S)-1-hydroxy-3-oxo-3-phenylpropyl]cyclopropane | 763126-70-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S,2R)-2-tert-butyldiphenylsilyloxymethyl-1-[(S)-1-hydroxy-3-oxo-3-phenylpropyl]cyclopropane
• CAS: 763126-70-1
• 化学式: C₂₉H₃₄O₃Si
• 分子量: 458.673
• InChiKey: SGNPXRIMGJLXBI-WSHBGFIESA-N

物化性质

• 沸点：
  552.3±46.0 °C(predicted)
• 密度：
  1.12±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.83
• 重原子数：
  33.0
• 可旋转键数：
  9.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  46.53
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (S)-(-)-α-甲氧基-α-(三氟甲基)苯乙酸 、 (1S,2R)-2-tert-butyldiphenylsilyloxymethyl-1-[(S)-1-hydroxy-3-oxo-3-phenylpropyl]cyclopropane 在 4-二甲氨基吡啶 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以100%的产率得到(S)-3,3,3-Trifluoro-2-methoxy-2-phenyl-propionic acid (S)-1-[(1S,2R)-2-(tert-butyl-diphenyl-silanyloxymethyl)-cyclopropyl]-3-oxo-3-phenyl-propyl ester
  参考文献：
  名称：

  The unusual 1,4-chelation-controlled nucleophilic addition to aldehydes with high stereoselectivity. A systematic study of stereoselectivity in the addition reaction of carbon nucleophiles to cis-substituted cyclopropanecarbaldehydes

  摘要：

  The addition reaction of carbon nucleophiles to cis-substituted cyclopropanecarbaldehydes was systematically investigated. Ab initio calculations of model cyclopropanecarbaldehydes suggested that the bisected s-cis and s-trans conformers are the only two minimum energy conformers, which are stabilized due to the pi-donating stereoelectronic effect of the cyclopropane ring. The experimental results of a series of substrates, that is, cyclopropanecarbaldehydes 1-5 bearing a cis-(tert-butyldiphenyisilyloxy)methyl group, a cis-benzyloxymethyl group, a cis-(p-methoxybenzyloxy)methyl group, cis-N,N-diethylcarbamoyl and trans-phenyl groups, and cis-(tert-butyldiphenylsilyloxy)methyl and trans-phenyl groups, respectively, showed that highly anti-selective Grignard additions could be realized. It turned out that it occurred via an unusual 7-membered 1,4-chelation-controlled pathway. Highly stereoselective Grignard addition via the chelation-controlled pathway occurred even in the reaction of the usually non-chelating silyl ether-type substrate 5. The results have great importance because the 1,4-chelation-controlled stereoselective addition reactions can indeed be realized. Under non-chelation conditions, the syn-products were produced with moderate stereoselectivity, which are likely to be formed via the bisected s-cis conformation-like transition state stabilized by the characteristic orbital interaction. These reactions, especially the chelation-controlled reaction, should be useful because of their t stereoselectivity and stereochemical predictability. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2004.05.063
• 作为产物：
  描述：

  1-苯基-1-三甲基硅氧乙烯 、 (1S,2R)-2-(((叔丁基二苯基硅烷基)氧基)甲基)环丙烷-1-甲醛 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以18 mg的产率得到(1S,2R)-2-tert-butyldiphenylsilyloxymethyl-1-[(S)-1-hydroxy-3-oxo-3-phenylpropyl]cyclopropane
  参考文献：
  名称：

  The unusual 1,4-chelation-controlled nucleophilic addition to aldehydes with high stereoselectivity. A systematic study of stereoselectivity in the addition reaction of carbon nucleophiles to cis-substituted cyclopropanecarbaldehydes

  摘要：

  The addition reaction of carbon nucleophiles to cis-substituted cyclopropanecarbaldehydes was systematically investigated. Ab initio calculations of model cyclopropanecarbaldehydes suggested that the bisected s-cis and s-trans conformers are the only two minimum energy conformers, which are stabilized due to the pi-donating stereoelectronic effect of the cyclopropane ring. The experimental results of a series of substrates, that is, cyclopropanecarbaldehydes 1-5 bearing a cis-(tert-butyldiphenyisilyloxy)methyl group, a cis-benzyloxymethyl group, a cis-(p-methoxybenzyloxy)methyl group, cis-N,N-diethylcarbamoyl and trans-phenyl groups, and cis-(tert-butyldiphenylsilyloxy)methyl and trans-phenyl groups, respectively, showed that highly anti-selective Grignard additions could be realized. It turned out that it occurred via an unusual 7-membered 1,4-chelation-controlled pathway. Highly stereoselective Grignard addition via the chelation-controlled pathway occurred even in the reaction of the usually non-chelating silyl ether-type substrate 5. The results have great importance because the 1,4-chelation-controlled stereoselective addition reactions can indeed be realized. Under non-chelation conditions, the syn-products were produced with moderate stereoselectivity, which are likely to be formed via the bisected s-cis conformation-like transition state stabilized by the characteristic orbital interaction. These reactions, especially the chelation-controlled reaction, should be useful because of their t stereoselectivity and stereochemical predictability. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2004.05.063