(S,E)-3-(but-2-enoyl)-4-isopropyl-5,5-dimethyloxazolidin-2-one | 909731-28-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: (S,E)-3-(but-2-enoyl)-4-isopropyl-5,5-dimethyloxazolidin-2-one
• 英文别名: (4S)-3-[(E)-but-2-enoyl]-5,5-dimethyl-4-propan-2-yl-1,3-oxazolidin-2-one
• CAS: 909731-28-8
• 化学式: C₁₂H₁₉NO₃
• 分子量: 225.288
• InChiKey: KLVAJUOXXUVCGW-FGEFZZPRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S,E)-3-(but-2-enoyl)-4-isopropyl-5,5-dimethyloxazolidin-2-one 在 三氟甲磺酸二丁硼 、 三乙胺 、 水 、 氯化铵 作用下， 以 二氯甲烷 、 四氢呋喃 为溶剂， 反应 0.5h， 以100%的产率得到(S)-3-(but-3-enoyl)-4-isopropyl-5,5-dimethyloxazolidin-2-one
  参考文献：
  名称：

  The dienolate aldol reaction of (E)-N-crotonoyl C(4)-isopropyl SuperQuat: asymmetric synthesis of α-vinyl-β-hydroxycarboxylic acid derivatives and conversion to α-ethylidene-β-hydroxyesters (β-substituted Baylis–Hillman products)

  摘要：

  The synthesis of alpha-vinyl-beta-hydroxyesters and alpha-ethlylidene-beta-hydroxyesters (beta-substituted Baylis-Hillman products) Via the dienolate aldol reaction of (E)-N-crotonoyl C(4)-isopropyl SuperQuat is described. High levels of syn-diastereoselectivity (up to >98% de) are observed for the dienolate aldol reaction with boron enolates, generated either directly with Bu2BOTf or by transmetalation of the potassium enolate with B-bromocatecholborane. Cleavage of the resultant syn-aldol products from the auxiliary gives alpha-vinyl-beta-hydroxyesters in >98% de and >98% ee. Subsequent isomerisation of the double bond into conjugation provides alpha-ethylidene-beta-hydroxyesters (beta-substituted Baylis-Hillman products) in high diastereo- and enantiopurity (>= 91:9 |(E):(Z)| and >98% ee). (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2009.07.004
• 作为产物：
  描述：

  在 正丁基锂 、 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 反应 6.0h， 生成 (S,E)-3-(but-2-enoyl)-4-isopropyl-5,5-dimethyloxazolidin-2-one
  参考文献：
  名称：

  Stereoselective α-Fluorination of N-Acyloxazolidinones at Room Temperature within 1 h

  摘要：

  A direct alpha-fluorination of N-acyloxazolidinones based on the unique reactivity of group IVa metal enolates has been developed. The reaction is an experimentally simple, low-cost, quick, and energy-efficient alternative for asymmetric alpha-fluorination of N-acyloicazolidinones. Preliminary studies have shown compatibility with alkyl, alkenyl, and alkynyl, aromatic, and several heteroaromatic substituents. High diastereoselectivities have been achieved with most substrates tested, and the reaction is typically complete within 1 h at ambient temperature.

  DOI：

  10.1021/jo500957d

文献信息

• Synthesis of the Acyclic Carbon Skeleton of Filipin III
  作者：Elodie Brun、Véronique Bellosta、Janine Cossy

  DOI：10.1021/acs.joc.6b01166

  日期：2016.9.16

  The synthesis of the carbon skeleton of filipin III, a polyenic macrolactone possessing 11 stereogenic centers, was achieved using a convergent strategy with the longest linear sequence of 19 steps starting from hexanal. Construction of the polyene was realized using two successive Heck couplings as the key steps. Control of the stereogenic centers of the polyol fragment was performed by utilizing

  使用会聚策略以最长的线性序列（从己醛开始）为中心的19个步骤，合成了具有11个立体异构中心的多烯型大内酯-菲利普斯III的碳骨架。使用两个连续的Heck偶联作为关键步骤，实现了多烯的构建。物用埃文斯醛醇缩合，1,3-执行的多元醇片段的立体中心的控制顺醛醇缩合，对映和非对映选择性烯丙基化，一个hemiacetalization /氧杂迈克尔序列，和1,3-顺式减少。多元醇与多烯片段使用1,5-耦合反非对映选择性醛醇缩合，随后由1,3-反减少。
• SuperQuat 5,5-dimethyl-4-iso-propyloxazolidin-2-one as a mimic of Evans 4-tert-butyloxazolidin-2-one
  作者：Steven D. Bull、Stephen G. Davies、A. Christopher Garner、Dennis Kruchinin、Min-Suk Key、Paul M. Roberts、Edward D. Savory、Andrew D. Smith、James E. Thomson

  DOI：10.1039/b605244d

  日期：——

  The incorporation of a gem-dimethyl group at the 5-position of a chiral oxazolidinone biases the conformation of the adjacent C(4)-stereodirecting group such that the gem-dimethyl-4-iso-propyl combination mimics a C(4)-tert-butyl group, providing higher levels of stereocontrol than a simple 4-iso-propyloxazolidinone. The generality of this principle is demonstrated with applications in stereoselective enolate alkylations, kinetic resolutions, Diels–Alder cycloadditions and Pd-catalysed asymmetric acetalisation reactions.

  在手性噁唑啉酮的5位引入一个双甲基基团会使得邻近的C(4)立体导向基团倾向于特定构象，即双甲基-4-异丙基的组合能模拟一个C(4)叔丁基基团，从而实现更高的立体控制水平，优于简单的4-异丙基噁唑啉酮。这一原理的普遍性在立体选择性烯醇化物烷基化、动力学拆分、狄尔斯-阿尔德环加成和钯催化的不对称缩醛化反应中得到了应用验证。
• A Difluoromethylene Linchpin/Synthon: Application in Conjunction with Anion Relay Chemistry (ARC) Permits Ready Access to Diverse Difluoromethylene Scaffolds
  作者：Kevin T. O’Brien、Jonathan W. Nadraws、Amos B. Smith

  DOI：10.1021/acs.orglett.0c03508

  日期：2021.3.5

  difluoromethylene scaffolds. Initiated via [1,2]-addition of an organolithium reagent to a β-difluoromethylene silyl aldehyde, an alkoxide intermediate is formed, which is capable of undergoing a [1,4]-Brook rearrangement to generate a stabilized α-difluoromethylene carbanion, which, upon electrophile capture, affords a three-component adduct. This three component synthetic tactic represents a novel one-pot

  有机二氟合成子与三组分非对映选择性阴离子中继化学 (ARC) 相结合，可以方便地使用各种二氟亚甲基支架。通过将有机锂试剂与 β-二氟亚甲基甲硅烷基醛 [1,2]-加成引发，形成醇盐中间体，该中间体能够进行 [1,4]-Brook 重排以产生稳定的 α-二氟亚甲基碳负离子，它在亲电捕获后提供三组分加合物。这种三组分合成策略代表了一种新的一锅发散策略，用于构建不同的有机二氟化合物。
• Total Synthesis of (+)-Lophirone H and Its Pentamethyl Ether Utilizing an Oxonium–Prins Cyclization
  作者：Hossay Abas、Sean M. Linsdall、Mathias Mamboury、Henry S. Rzepa、Alan C. Spivey

  DOI：10.1021/acs.orglett.7b00642

  日期：2017.5.19

  The first total synthesis of (+)-lophirone H (1) and its pentamethyl ether 29, featuring an oxonium–Prins cyclization/benzylic cation trapping reaction, is described.

  描述了（+）-lophirone H（1）及其五甲基醚29的第一个全合成，其特征在于具有氧鎓-普林斯环化/苄基阳离子捕集反应。