(R)-(E)-tert-Butyl 5-(tert-Butyldimethylsiloxy)-4-methyl-2-pentenoate | 138877-99-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (R)-(E)-tert-Butyl 5-(tert-Butyldimethylsiloxy)-4-methyl-2-pentenoate
• 英文别名: tert-butyl (E,4R)-5-[tert-butyl(dimethyl)silyl]oxy-4-methylpent-2-enoate
• CAS: 138877-99-3
• 化学式: C₁₆H₃₂O₃Si
• 分子量: 300.514
• InChiKey: HWJBGXPAHCHZNI-OCHBPSSRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.54
• 重原子数：
  20
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (R)-(E)-tert-Butyl 5-(tert-Butyldimethylsiloxy)-4-methyl-2-pentenoate 在 palladium dihydroxide 正丁基锂 、 氢气 作用下， 以 乙酸乙酯 为溶剂， 反应 26.0h， 生成 (3S,4R)-tert-Butyl 3-Amino-5-(tert-butyldimethylsiloxy)-4-methylpentanoate
  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：

  (S)-3-(tert-butyldimethylsilyloxy)-2-methylpropionic acid methyl ester 在 二异丁基氢化铝 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 4.5h， 生成 (R)-(E)-tert-Butyl 5-(tert-Butyldimethylsiloxy)-4-methyl-2-pentenoate
  参考文献：
  名称：

  A Three Component Coupling Approach to a Chiral 1.beta.-Methylcarbapenem Key Intermediate

  摘要：

  Conjugate addition of N-benzyl-N((R)-1-phenylethyl)amine (R)-5 to (R)-(E)-tert-butyl 5-((tert-butyldimethylsilyl)oxy)-4-methyl-2-pentenoate (10a) produced the (3S,4R)-syn-adduct 14 with essentially 100% de in 84% yield, whereas the addition of (S)-5 to 10a afforded the (3R,4R)-anti-adduct 15 with essentially 100% de in 95% yield. The syn adduct 14 was converted upon sequential treatment with lithium diisopropylamide-methylaluminum dichloride-acetaldehyde to the key intermediate 21; the diastereoisomer ratio of 21 to other diasteroisomers was 80:20. Conversion of 21 to a 1 beta-methylcarbapenem key intermediate 26 was carried out readily according to the known procedures.

  DOI：

  10.1021/jo00106a027

文献信息

• An asymmetric ammonia synthon for Michael additions
  作者：Joel M. Hawkins、Timothy A. Lewis

  DOI：10.1021/jo00033a037

  日期：1992.3

  The highly diastereoselective 1,4-addition of lithiated chiral amine 1 to alpha,beta-unsaturated esters, followed by hydrogenolysis of the benzylic-type C-N bonds of the 1,4-adducts, provides an asymmetric ammonia synthon for Michael additions. Under optimized conditions, lithiated 1 adds to alpha,beta-unsaturated tert-butyl esters in dimethoxyethane at -63-degrees-C in high yield with very high diastereoselectivity. Small, large, functionalized, and chiral beta-ester substituents are amenable, with (S)-1 consistently adding to (E)-3 from the top as drawn in Table II. Hydrogenolysis liberates the beta-amino esters with typically 95-99% ee.
• A stereocontrolled approach to 1β-methylcarbapenem
  作者：Stephen G. Davies、Charles J.R. Hedgecock、Jeffrey M. McKenna

  DOI：10.1016/0957-4166(95)00079-5

  日期：1995.4

  Conjugate addition of lithium N-allyl-N-alpha-methylbenzylamide to chiral alpha,beta-unsaturated esters is subject to double stereodifferentiation, the mismatched pair reaction allowing access to an intermediate for 1 beta-methylcarbapenem synthesis.
• Highly Diastereoselective Conjugate Addition of Lithium Dialkylamides to α,β-Unsaturated Esters Having a Chiral Center at the γ-Position
  作者：Naoki Asao、Takashi Shimada、Tomoko Sudo、Naofumi Tsukada、Kazuhiko Yazawa、Young Soo Gyoung、Tadao Uyehara、Yoshinori Yamamoto

  DOI：10.1021/jo970435d

  日期：1997.9.1

  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).
• A Three Component Coupling Approach to a Chiral 1.beta.-Methylcarbapenem Key Intermediate
  作者：Naofumi Tsukada、Takashi Shimada、Young Soo Gyoung、Naoki Asao、Yoshinori Yamamoto

  DOI：10.1021/jo00106a027

  日期：1995.1

  Conjugate addition of N-benzyl-N((R)-1-phenylethyl)amine (R)-5 to (R)-(E)-tert-butyl 5-((tert-butyldimethylsilyl)oxy)-4-methyl-2-pentenoate (10a) produced the (3S,4R)-syn-adduct 14 with essentially 100% de in 84% yield, whereas the addition of (S)-5 to 10a afforded the (3R,4R)-anti-adduct 15 with essentially 100% de in 95% yield. The syn adduct 14 was converted upon sequential treatment with lithium diisopropylamide-methylaluminum dichloride-acetaldehyde to the key intermediate 21; the diastereoisomer ratio of 21 to other diasteroisomers was 80:20. Conversion of 21 to a 1 beta-methylcarbapenem key intermediate 26 was carried out readily according to the known procedures.