tert-butyl (2E,4S,5R)-4,5-O-isopropylidene-hepta-2,6-dienoate | 1085845-83-5

• 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-hepta-2,6-dienoate
• 英文别名: tert-butyl (4S,5R,E)-4,5-O-isopropylidenehepta-2,6-dienoate；tert-butyl (E)-3-[(4S,5R)-5-ethenyl-2,2-dimethyl-1,3-dioxolan-4-yl]prop-2-enoate
• CAS: 1085845-83-5
• 化学式: C₁₄H₂₂O₄
• 分子量: 254.326
• InChiKey: QBYRSQWDGGHHKV-OJLMFNQTSA-N

物化性质

• 沸点：
  328.2±37.0 °C(predicted)
• 密度：
  1.079±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  tert-butyl (2E,4S,5R)-4,5-O-isopropylidene-hepta-2,6-dienoate 在 Grubbs catalyst first generation 、 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 24.0h， 生成 tert-butyl (2R,2'S,3'S,4'R,αR,Z)-2-hydroxy-2-[N(1')-α-methylbenzyl-3',4'-O-isopropylidene-1',2',3',4',7',8'-hexahydroazocin-2'-yl]ethanoate
  参考文献：
  名称：

  Asymmetric Synthesis of Polyhydroxylated Pyrrolizidines via Transannular Iodoamination with Concomitant N-Debenzylation

  摘要：

  The doubly diastereoselective "matched" conjugate addition of lithium (R)-N-but-3-enyl-N-(alpha-methyl-p-methoxybenzyl)amide to tert-butyl (4S,5R,E)-4,5-O-isopropylidene-2,7-dienoate (derived from D-ribose in 3 steps) and in situ enolate oxidation with (-)-camphorsulfonyloxaziridine was followed by ring-closing metathesis with Grubbs 1 to give a hexahydroazocine scaffold. Subsequent treatment with I-2 resulted in transannular Iodoamination accompanied by loss of the alpha-methyl-p-methoxybenzyl group to give the corresponding pyrrolizidine scaffold as a single diastereoisomer upon direct crystallization from the crude reaction mixture. Further functional group manipulations enabled the preparation of (-)-7a-epi-hyacinthacine A1.

  DOI：

  10.1021/ol103090z
• 作为产物：
  描述：

  卡培他滨杂质25 在 咪唑 、 盐酸 、 正丁基锂 、 碘 、 三苯基膦 作用下， 以 乙醚 、 正己烷 、 水 、 甲苯 、 乙腈 为溶剂， 反应 1.0h， 生成 tert-butyl (2E,4S,5R)-4,5-O-isopropylidene-hepta-2,6-dienoate
  参考文献：
  名称：

  Asymmetric Synthesis of Polyhydroxylated Pyrrolizidines via Transannular Iodoamination with Concomitant N-Debenzylation

  摘要：

  The doubly diastereoselective "matched" conjugate addition of lithium (R)-N-but-3-enyl-N-(alpha-methyl-p-methoxybenzyl)amide to tert-butyl (4S,5R,E)-4,5-O-isopropylidene-2,7-dienoate (derived from D-ribose in 3 steps) and in situ enolate oxidation with (-)-camphorsulfonyloxaziridine was followed by ring-closing metathesis with Grubbs 1 to give a hexahydroazocine scaffold. Subsequent treatment with I-2 resulted in transannular Iodoamination accompanied by loss of the alpha-methyl-p-methoxybenzyl group to give the corresponding pyrrolizidine scaffold as a single diastereoisomer upon direct crystallization from the crude reaction mixture. Further functional group manipulations enabled the preparation of (-)-7a-epi-hyacinthacine A1.

  DOI：

  10.1021/ol103090z

文献信息

• Highly (<i>E</i>)-Selective Wadsworth−Emmons Reactions Promoted by Methylmagnesium Bromide
  作者：Timothy D. W. Claridge、Stephen G. Davies、James A. Lee、Rebecca L. Nicholson、Paul M. Roberts、Angela J. Russell、Andrew D. Smith、Steven M. Toms

  DOI：10.1021/ol802212e

  日期：2008.12.4

  An experimentally simple protocol for the very highly (E)-selective Wadsworth-Emmons reaction [(E):(Z) selectivities in excess of 180:1 in some cases] of a range of straight-chain and branched aliphatic, substituted aromatic, and base-sensitive aldehydes via reaction with an alkyl diethylphosphonoacetate and MeMgBr is reported.

  对一系列直链和支链脂族，取代芳族化合物进行非常高度（E）选择性的Wadsworth-Emmons反应[（E）:( Z）选择性在某些情况下超过180：1的反应）的实验简单方法，报道了通过与烷基二乙基膦酰基乙酸酯和MeMgBr反应生成的对碱敏感的醛。
• 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。
• Iodine-mediated Ring Closing Alkene Iodoamination with N-Debenzylation for the Asymmetric Synthesis of Polyhydroxylated Pyrrolidines
  作者：Stephen G. Davies、Rebecca L. Nicholson、Paul D. Price、Paul. M. Roberts、Andrew D. Smith

  DOI：10.1055/s-2004-820031

  日期：——

  An iodine-mediated ring closing alkene iodoamination with N-debenzylation protocol provides a direct route for the asymmetric synthesis of polyhydroxylated pyrrolidines from homochiral β-amino acid derivatives.

  碘介导的闭环烯烃碘胺化与 N-脱苄基化方案为从同手性 β-氨基酸衍生物不对称合成多羟基吡咯烷提供了直接途径。
• Asymmetric Synthesis of Polyhydroxylated Pyrrolizidines via Transannular Iodoamination with Concomitant <i>N</i>-Debenzylation
  作者：E. Anne Brock、Stephen G. Davies、James A. Lee、Paul M. Roberts、James E. Thomson

  DOI：10.1021/ol103090z

  日期：2011.4.1

  The doubly diastereoselective "matched" conjugate addition of lithium (R)-N-but-3-enyl-N-(alpha-methyl-p-methoxybenzyl)amide to tert-butyl (4S,5R,E)-4,5-O-isopropylidene-2,7-dienoate (derived from D-ribose in 3 steps) and in situ enolate oxidation with (-)-camphorsulfonyloxaziridine was followed by ring-closing metathesis with Grubbs 1 to give a hexahydroazocine scaffold. Subsequent treatment with I-2 resulted in transannular Iodoamination accompanied by loss of the alpha-methyl-p-methoxybenzyl group to give the corresponding pyrrolizidine scaffold as a single diastereoisomer upon direct crystallization from the crude reaction mixture. Further functional group manipulations enabled the preparation of (-)-7a-epi-hyacinthacine A1.