(1'S,2R,4''R)-2-[(2,2-dimethyl-[1,3]dioxolan-4-yl)(trimethylsilanyloxy)methyl]-5-oxo-2,5-dihydro-1H-pyrrole-1-carboxylic acid tert-butyl ester | 141293-16-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯啉
• 英文名称: (1'S,2R,4''R)-2-[(2,2-dimethyl-[1,3]dioxolan-4-yl)(trimethylsilanyloxy)methyl]-5-oxo-2,5-dihydro-1H-pyrrole-1-carboxylic acid tert-butyl ester
• 英文别名: (4R,5S,6R)-N-tert-butoxycarbonyl-5-O-trimethylsilyl-6,7-O-isopropylidene-2,3-dideoxy-hept-2-enono-1,4-lactam；(5R)-1-(tert-butoxycarbonyl)-5-{(S)-trimethylsilanyloxy[(R)-2,2-dimethyl-1,3-dioxolan-4-yl]methyl}-1H-pyrrol-2(5H)-one；tert-butyl (2R)-2-[(S)-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-trimethylsilyloxymethyl]-5-oxo-2H-pyrrole-1-carboxylate
• CAS: 141293-16-5
• 化学式: C₁₈H₃₁NO₆Si
• 分子量: 385.533
• InChiKey: DTRVGCCVWNIZFY-NFAWXSAZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.06
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  74.3
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (1'S,2R,4''R)-2-[(2,2-dimethyl-[1,3]dioxolan-4-yl)(trimethylsilanyloxy)methyl]-5-oxo-2,5-dihydro-1H-pyrrole-1-carboxylic acid tert-butyl ester 在 palladium on activated charcoal 2,6-二甲基吡啶 、 正丁基锂 、 ammonium cerium(IV) nitrate 、 二苯基二硒醚 、 氢气 、 sodium acetate 、 柠檬酸 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 乙酸乙酯 、 乙腈 为溶剂， 反应 29.0h， 生成 (1^IS,1^IIIS,3S,4^IIR,4^IVR,5R)-3,5-bis[(tert-butyldimethylsilanyloxy)(2,2-dimethyl-[1,3]dioxolan-4-yl)methyl]-pyrrolidin-2-one
  参考文献：
  名称：

  New Enantioselective Entry to Cycloheptane Amino Acid Polyols

  摘要：

  A diversity-oriented protocol has been developed for the assembly of densely hydroxylated cycloheptane amino acids via succession of a vinylogous Mukaiyama aldol reaction (VMAR), a Morita-Baylis-Hillman reaction (MBHR), and an intramolecular pinacol coupling reaction (IPCR). The plan utilizes Dor L-configured glyceraldehyde derivatives as "chiral" surrogates of glyoxal and N-[(tert-butoxycarbonyl)2-(tert-butyldimethylsilyl)oxy]pyrrole as the synthetic equivalent of the alpha,gamma-dianion of gamma-aminobutanoic acid. The parallel, asymmetric syntheses of four cycloheptane representatives proceed with high diastereocontrol and virtually complete enantioselectivity in ten steps and overall yields of 15-37%.

  DOI：

  10.1021/jo0520137
• 作为产物：
  描述：

  N-(tert-butoxycarbonyl)-2-[(tert-butyldimethylsilyl)oxy]pyrrole 在 吡啶 、 四氯化锡 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 3.0h， 生成 (1'S,2R,4''R)-2-[(2,2-dimethyl-[1,3]dioxolan-4-yl)(trimethylsilanyloxy)methyl]-5-oxo-2,5-dihydro-1H-pyrrole-1-carboxylic acid tert-butyl ester
  参考文献：
  名称：

  New Enantioselective Entry to Cycloheptane Amino Acid Polyols

  摘要：

  A diversity-oriented protocol has been developed for the assembly of densely hydroxylated cycloheptane amino acids via succession of a vinylogous Mukaiyama aldol reaction (VMAR), a Morita-Baylis-Hillman reaction (MBHR), and an intramolecular pinacol coupling reaction (IPCR). The plan utilizes Dor L-configured glyceraldehyde derivatives as "chiral" surrogates of glyoxal and N-[(tert-butoxycarbonyl)2-(tert-butyldimethylsilyl)oxy]pyrrole as the synthetic equivalent of the alpha,gamma-dianion of gamma-aminobutanoic acid. The parallel, asymmetric syntheses of four cycloheptane representatives proceed with high diastereocontrol and virtually complete enantioselectivity in ten steps and overall yields of 15-37%.

  DOI：

  10.1021/jo0520137

文献信息

• Vicarious Silylative Mukaiyama Aldol Reaction: A Vinylogous Extension
  作者：Claudio Curti、Andrea Sartori、Lucia Battistini、Gloria Rassu、Paola Burreddu、Franca Zanardi、Giovanni Casiraghi

  DOI：10.1021/jo800741c

  日期：2008.7.1

  A vinylogous, silylative, and direct variant of the venerable Mukaiyama aldol reaction has been developed. Exploiting N-Boc-pyrrol-2(5H)-one as the conjugate donor, several aldehyde and ketone acceptors were scrutinized under the guidance of suitable dual Lewis acid-Lewis base activators to provide a varied repertoire of functionality-rich alpha,beta-unsaturated-gamma-amino-delta-silyloxy carbonyl structures, in useful yields and often with an exquisite level of diastereoselection.
• N-(tert-Butoxycarbonyl)-2-(tert-butyldimethylsiloxy)pyrrole: a promising compound for synthesis of chiral nonracemic hydroxylated pyrrolidine derivatives
  作者：Giovanni Casiraghi、Gloria Rassu、Pietro Spanu、Luigi Pinna

  DOI：10.1021/jo00040a006

  日期：1992.7

  N-t-Boc-2-(tert-butyldimethylsiloxy)pyrrole has been synthesized from pyrrole and used to prepare enantiomerically pure pyrrolinones 5, 6, 15, and 16 and polyhydroxylated pyrrolidinones of type 11 and 12.
• Homochiral α,β-unsaturated γ-lactams: Versatile templates
  作者：Gloria Rassu、Giovanni Casiraghi、Pietro Spanu、Luigi Pinna、Giovanna Gasparri Fava、Marisa Belicchi Ferrari、Giorgio Pelosi

  DOI：10.1016/s0957-4166(00)86037-1

  日期：1992.8

  The enantiomerically pure crystalline alpha,beta-unsaturated gamma-lactams 4 and 5 have been synthesized by utilizing 2,3-O-isopropylidene-D-glyceraldehyde (3) as chiral source and novel N-tert-butoxycarbonyl-2-(tert-butyldimethylsiloxy)pyrrole (TBSOP) as four carbon homologative reagent. Unsaturated lactam 4 has been selectively elaborated into hydroxylated pyrrolidiones 7,8, and 11 by stereocontrolled procedures involving conjugate addition of organocuprates, cis-dihydroxylation, and alpha-alkylation via hydrogenation and enolate formation. The absolute stereochemistries of 4 and 5 have been secured by single crystal X-ray analyses.
• New Enantioselective Entry to Cycloheptane Amino Acid Polyols
  作者：Claudio Curti、Franca Zanardi、Lucia Battistini、Andrea Sartori、Gloria Rassu、Luciana Auzzas、Annamaria Roggio、Luigi Pinna、Giovanni Casiraghi

  DOI：10.1021/jo0520137

  日期：2006.1.1

  A diversity-oriented protocol has been developed for the assembly of densely hydroxylated cycloheptane amino acids via succession of a vinylogous Mukaiyama aldol reaction (VMAR), a Morita-Baylis-Hillman reaction (MBHR), and an intramolecular pinacol coupling reaction (IPCR). The plan utilizes Dor L-configured glyceraldehyde derivatives as "chiral" surrogates of glyoxal and N-[(tert-butoxycarbonyl)2-(tert-butyldimethylsilyl)oxy]pyrrole as the synthetic equivalent of the alpha,gamma-dianion of gamma-aminobutanoic acid. The parallel, asymmetric syntheses of four cycloheptane representatives proceed with high diastereocontrol and virtually complete enantioselectivity in ten steps and overall yields of 15-37%.