tert-butyl (2E,4S,5R)-4,5-O-isopropylidene-6-(tert-butyldimethylsilyloxy)hex-2-enoate | 1137951-71-3

• 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: tert-butyl (2E,4S,5R)-4,5-O-isopropylidene-6-(tert-butyldimethylsilyloxy)hex-2-enoate
• 英文别名: tert-butyl (E)-3-[(4S,5S)-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-2,2-dimethyl-1,3-dioxolan-4-yl]prop-2-enoate
• CAS: 1137951-71-3
• 化学式: C₁₉H₃₆O₅Si
• 分子量: 372.577
• InChiKey: ISYOKZKAQNJFOE-NOQIOLJMSA-N

物化性质

• 沸点：
  410.4±40.0 °C(predicted)
• 密度：
  0.988±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.43
• 重原子数：
  25
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.84
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  tert-butyl (2E,4S,5R)-4,5-O-isopropylidene-6-(tert-butyldimethylsilyloxy)hex-2-enoate 在 吡啶 、 正丁基锂 、 四丁基氟化铵 、 甲基磺酰氯 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 64.5h， 生成 tert-butyl (S)-2,6-anhydro-3-deoxy-3-[N-benzyl-N-(α-methylbenzyl)amino]-4,5-O-isopropylidene-L-gulonate
  参考文献：
  名称：

  Stereospecific Cyclization Strategies for α,ε-Dihydroxy-β-amino Esters: Asymmetric Syntheses of Imino and Amino Sugars

  摘要：

  A range of biologically significant imino and amino sugars [1,4-dideoxy-1,4-imino-D-allitol, 3,6-dideoxy-3,6-imino-L-allonic acid, (3R,4S)-3,4-dihydroxy-L-proline, 1,5-anhydro-4-deoxy-4-amino-D-glucitol, and 1,5-anhydro-4-deoxy-4-amino-L-iditol] has been prepared via stereospecific cyclization of alpha,epsilon-dihydroxy-beta-amino esters. These substrates are readily prepared via conjugate addition of lithium (S)-N-benzyl-N-(alpha-methylbenzyl)amide to enantiopure alpha,beta-unsaturated esters (beta-substituted with cis- and trans-dioxolane units) coupled with in situ enolate oxidation with camphorsulfonyloxaziridine (CSO). Activation of the epsilon-hydroxyl group allowed cyclization to either the corresponding pyrrolidine or the tetrahydropyran scaffold, with the course of the cyclization process being dictated by the relative configuration of the dioxolane unit. When the alpha,epsilon-dihydroxy-beta-amino ester bears a cis-dioxolane unit, cyclization occurs upon attack of the beta-amino substituent to give the corresponding pyrrolidine after in situ N-debenzylation. In contrast, when the alpha,epsilon-dihydroxy-beta-amino ester bears a trans-dioxolane unit, cyclization occurs upon attack of the alpha-hydroxyl substituent to give the corresponding tetrahydropyran.

  DOI：

  10.1021/jo5018298
• 作为产物：
  描述：

  二乙基膦酰基乙酸叔丁酯 、 (4R,5S)-5-tert-butyldimethylsilyloxymethyl-2,2-dimethyl-1,3-dioxolane-4-carbaldehyde 在 甲基溴化镁 作用下， 以 四氢呋喃 为溶剂， 反应 2.5h， 以160 mg的产率得到tert-butyl (2E,4S,5R)-4,5-O-isopropylidene-6-(tert-butyldimethylsilyloxy)hex-2-enoate
  参考文献：
  名称：

  将同手性锂酰胺双非对映选择性共轭加成到含有顺式和反式二氧戊环单元的纯手性α，β-不饱和酯中†

  摘要：

  作为针对非天然氨基糖从头开始不对称合成的长期目标的一部分，对映体的对映体的双非对映选择性共轭加成反应锂Ñ苄基ñ - （α -甲基苄基）酰胺研究了一系列含有顺式和反式二氧戊环单元的同质手性α，β-不饱和酯。这些反应导致“匹配”和“不匹配”效应。在“匹配”情况下，会生成相应的β-氨基酯的单个非对映异构体（包含三个连续的立体中心）。共轭添加到含有顺式-二氧戊环单元的纯手性α，β-不饱和酯时，在“不匹配”的情况下，底物的立体控制高于酰胺锂，而添加到纯手性的α，β中含有反式-二氧戊环单元的-不饱和酯，主要是对手性锂酰胺的立体控制。氢解氮缀合物加成的β-氨基酯产物的-脱保护得到了多氧化的β-氨基酸衍生物。

  DOI：

  10.1039/b818298a

文献信息

• Doubly diastereoselective conjugate addition of homochiral lithium amides to homochiral α,β-unsaturated esters containing cis- and trans-dioxolane units
  作者：Stephen G. Davies、Matthew J. Durbin、Euan C. Goddard、Peter M. Kelly、Wataru Kurosawa、James A. Lee、Rebecca L. Nicholson、Paul D. Price、Paul M. Roberts、Angela J. Russell、Philip M. Scott、Andrew D. Smith

  DOI：10.1039/b818298a

  日期：——

  corresponding β-amino ester (containing three contiguous stereocentres) is produced. Upon conjugate addition to a homochiral α,β-unsaturated ester containing a cis-dioxolane unit, in the “mismatched” case it is the stereocontrol of the substrate which is dominant over that of the lithium amide, whilst upon addition to homochiral α,β-unsaturated esters containing a trans-dioxolane unit the stereocontrol of

  作为针对非天然氨基糖从头开始不对称合成的长期目标的一部分，对映体的对映体的双非对映选择性共轭加成反应锂Ñ苄基ñ - （α -甲基苄基）酰胺研究了一系列含有顺式和反式二氧戊环单元的同质手性α，β-不饱和酯。这些反应导致“匹配”和“不匹配”效应。在“匹配”情况下，会生成相应的β-氨基酯的单个非对映异构体（包含三个连续的立体中心）。共轭添加到含有顺式-二氧戊环单元的纯手性α，β-不饱和酯时，在“不匹配”的情况下，底物的立体控制高于酰胺锂，而添加到纯手性的α，β中含有反式-二氧戊环单元的-不饱和酯，主要是对手性锂酰胺的立体控制。氢解氮缀合物加成的β-氨基酯产物的-脱保护得到了多氧化的β-氨基酸衍生物。
• Stereospecific Cyclization Strategies for α,ε-Dihydroxy-β-amino Esters: Asymmetric Syntheses of Imino and Amino Sugars
  作者：Stephen G. Davies、Emma M. Foster、James A. Lee、Paul M. Roberts、James E. Thomson

  DOI：10.1021/jo5018298

  日期：2014.10.17

  A range of biologically significant imino and amino sugars [1,4-dideoxy-1,4-imino-D-allitol, 3,6-dideoxy-3,6-imino-L-allonic acid, (3R,4S)-3,4-dihydroxy-L-proline, 1,5-anhydro-4-deoxy-4-amino-D-glucitol, and 1,5-anhydro-4-deoxy-4-amino-L-iditol] has been prepared via stereospecific cyclization of alpha,epsilon-dihydroxy-beta-amino esters. These substrates are readily prepared via conjugate addition of lithium (S)-N-benzyl-N-(alpha-methylbenzyl)amide to enantiopure alpha,beta-unsaturated esters (beta-substituted with cis- and trans-dioxolane units) coupled with in situ enolate oxidation with camphorsulfonyloxaziridine (CSO). Activation of the epsilon-hydroxyl group allowed cyclization to either the corresponding pyrrolidine or the tetrahydropyran scaffold, with the course of the cyclization process being dictated by the relative configuration of the dioxolane unit. When the alpha,epsilon-dihydroxy-beta-amino ester bears a cis-dioxolane unit, cyclization occurs upon attack of the beta-amino substituent to give the corresponding pyrrolidine after in situ N-debenzylation. In contrast, when the alpha,epsilon-dihydroxy-beta-amino ester bears a trans-dioxolane unit, cyclization occurs upon attack of the alpha-hydroxyl substituent to give the corresponding tetrahydropyran.