(2S,3S,4S)-2-((R)-1-Acetoxy-ethyl)-3-benzylamino-4-(tert-butyl-diphenyl-silanyloxy)-pentanoic acid tert-butyl ester | 161554-86-5

• 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: (2S,3S,4S)-2-((R)-1-Acetoxy-ethyl)-3-benzylamino-4-(tert-butyl-diphenyl-silanyloxy)-pentanoic acid tert-butyl ester
• CAS: 161554-86-5
• 化学式: C₃₆H₄₉NO₅Si
• 分子量: 603.874
• InChiKey: FDLUXBOJUPWAOR-RJYGDKEGSA-N

物化性质

• 沸点：
  625.014±55.00 °C(Press: 760.00 Torr)(predicted)
• 密度：
  1.081±0.10 g/cm3(Temp: 25 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.02
• 重原子数：
  43.0
• 可旋转键数：
  12.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  73.86
• 氢给体数：
  1.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  (2S,3S,4S)-2-((R)-1-Acetoxy-ethyl)-3-benzylamino-4-(tert-butyl-diphenyl-silanyloxy)-pentanoic acid tert-butyl ester 在 2,2'-二硫二吡啶 、 三苯基膦 、 三氟乙酸 作用下， 生成 [(1R)-1-[(2S,3S)-1-benzyl-2-[(1S)-1-[tert-butyl(diphenyl)silyl]oxyethyl]-4-oxoazetidin-3-yl]ethyl] acetate
  参考文献：
  名称：

  Highly Diastereoselective Conjugate Addition of Lithium Dialkylamides to α,β-Unsaturated Esters Having a Chiral Center at the γ-Position

  摘要：

  The conjugate addition of lithium amides 2 to tert-butyl 4-(OR)-substituted-2-pentenoates 1 produced a mixture of the syn-and anti-amino esters (3 and 4) in high yields. Sterically bulky OR groups, such as trityloxy and tert-butyldiphenylsilyloxy, gave the syn diastereomer 3 either exclusively or predominantly. The syn-selectivity may be explained by a modified Felkin-Anh model. The use of tert-butyldimethylsilyloxy as an OR group afforded a nearly 1:1 mixture of diastereoisomers, and the use of the smallest MeO group produced a 63:37 mixture of the syn 3 and anti isomer 4. The presence of Me group at the alpha-position (C-2 position) of the enoate enhanced the syn diastereoselectivity up to 100%; the conjugate addition to tert-butyl 4-methoxy-2-methyl-2-pentenoate (17) gave the syn-isomer 18 exclusively. This enhancement may be explained by the combination of chelation and allylic strain model 19 in which the smallest H orients inside to avoid an allylic strain. A phenyl group at the gamma-position enhanced the anti selectivity in the case of gamma-alkoxy-alpha,beta-enoates such as isopropyl 4-[(tert-butyldimethylsilyl)oxy]-4-phenyl-2-buteonoate (20), and in the case of gamma-alkyl-alpha,beta-enoates such as tert-butyl 4-phenyl-2-pentenoate (27).

  DOI：

  10.1021/jo970435d
• 作为产物：
  描述：

  叔丁基二苯基氯硅烷 在 吡啶 、 咪唑 、 正丁基锂 、 sodium hydride 、 二异丁基氢化铝 、 lithium diisopropyl amide 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 11.16h， 生成 (2S,3S,4S)-2-((R)-1-Acetoxy-ethyl)-3-benzylamino-4-(tert-butyl-diphenyl-silanyloxy)-pentanoic acid tert-butyl ester
  参考文献：
  名称：

  Highly Diastereoselective Conjugate Addition of Lithium Dialkylamides to α,β-Unsaturated Esters Having a Chiral Center at the γ-Position

  摘要：

  The conjugate addition of lithium amides 2 to tert-butyl 4-(OR)-substituted-2-pentenoates 1 produced a mixture of the syn-and anti-amino esters (3 and 4) in high yields. Sterically bulky OR groups, such as trityloxy and tert-butyldiphenylsilyloxy, gave the syn diastereomer 3 either exclusively or predominantly. The syn-selectivity may be explained by a modified Felkin-Anh model. The use of tert-butyldimethylsilyloxy as an OR group afforded a nearly 1:1 mixture of diastereoisomers, and the use of the smallest MeO group produced a 63:37 mixture of the syn 3 and anti isomer 4. The presence of Me group at the alpha-position (C-2 position) of the enoate enhanced the syn diastereoselectivity up to 100%; the conjugate addition to tert-butyl 4-methoxy-2-methyl-2-pentenoate (17) gave the syn-isomer 18 exclusively. This enhancement may be explained by the combination of chelation and allylic strain model 19 in which the smallest H orients inside to avoid an allylic strain. A phenyl group at the gamma-position enhanced the anti selectivity in the case of gamma-alkoxy-alpha,beta-enoates such as isopropyl 4-[(tert-butyldimethylsilyl)oxy]-4-phenyl-2-buteonoate (20), and in the case of gamma-alkyl-alpha,beta-enoates such as tert-butyl 4-phenyl-2-pentenoate (27).

  DOI：

  10.1021/jo970435d

文献信息

• Highly stereocontrolled and concise asymmetric synthesis of the β-Lactam framework via a TCC method
  作者：Naoki Asao、Takashi Shimada、Naofumi Tsukada、Yoshinori Yamamoto

  DOI：10.1016/s0040-4039(00)74424-8

  日期：1994.11

  The conjugate addition of LSA 1 to t-butyl (4S)4-(trilyl)oxy-2-pentenoate 2d followed by aldol condensation with acetaldehyde produces a key intermediate 3 to beta-lactam derivatives as a single diastereoisomer in 77% yield.