(2S,3S)-2-phenyl-3-((prop-2-yn-1-yloxy)methyl)oxirane | 1202053-57-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2S,3S)-2-phenyl-3-((prop-2-yn-1-yloxy)methyl)oxirane
• 英文别名: (2S,3S)-2-phenyl-3-(prop-2-ynoxymethyl)oxirane
• CAS: 1202053-57-3
• 化学式: C₁₂H₁₂O₂
• 分子量: 188.226
• InChiKey: PERMHGJTJXHKQJ-RYUDHWBXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  21.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2S,3S)-2-phenyl-3-((prop-2-yn-1-yloxy)methyl)oxirane 在 ammonium hydroxide 、 lithium perchlorate 、 三乙胺 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 、 异丙醇 、 甲苯 为溶剂， 反应 43.0h， 生成
  参考文献：
  名称：

  A Recyclable, Immobilized Analogue of Benzotetramisole for Catalytic Enantioselective Domino Michael Addition/Cyclization Reactions in Batch and Flow

  摘要：

  A polystyrene-supported, enantiopure benzote-tramisole (BTM) analogue (5) has been synthesized from (2S,3S)-phenylglycidol through a five-step sequence involving a copper-catalyzed alkyne azide cycloaddition (CuAAC) reaction as the final, immobilization step. The functional resin 5 (f = 0.9 mmol g(-1)) has been successfully used as a highly active and enantioselective catalyst in the domino Michael addition/cyclization reaction of in situ activated arylacetic acids (7) with chalcone-type tosylimines (6), leading to dihydropyridinones 8 (17 examples) to afford the products with excellent yields and very high enantioselectivity (mean ee 97.4%). The deactivation of 5 by species present during the catalytic process has been studied, and pivaloyl chloride (required for the activation of the arylacetic acid) has been identified as the main source of deactivation. A simple experimental protocol taking this fact into account has allowed the multiple recycling of 5 with only a marginal decrease in catalytic activity and the implementation of a continuous flow process where the activation of phenylacetic acid (residence time 14.2 min), the asymmetric domino Michael addition/cydization reaction (residence time 7.5 min), and aqueous workup are performed sequentially, delivering the dihydropyridinone product as a clean dichloromethane solution (0.54 mmol catalyst sample; 11 h operation; 8a (4.44 g, >99.9% ee)). The supported catalyst 5 has also been used in a new domino Michael addition/cydization reaction involving saccharin-derived tosylimines 9 as electrophiles, leading to 8,9-dihydro-7H-benzo[4,5]isothiazolo [2,3-[a]pyridin-7-one 5,5-dioxides 10 (8 examples) in high isolated yields and diastereoselectivities and excellent enantioselectivities (mean ee 98%). A single sample of 5 (0.5 g, 0.45 mmol) has been used for the sequential preparation in batch of a library of 7 different derivatives 10 at the gram scale (ca. 10 g, accumulated TON = 51), the whole process being performed without any column chromatographic purification. The increased diastereoselectivity recorded with 5 in reactions involving sterically congested arylacetic acids (with respect to homogeneous BTM) has been rationalized through the occurrence of steric interactions between the sulfonylimine and the linker plus support catalyst fragments leading to additional destabilization of the transition state leading to the minor, cis diastereomer of products 8/10.

  DOI：

  10.1021/acscatal.5b02121
• 作为产物：
  描述：

  肉桂醇 在 L-(+)-酒石酸二乙酯 、 titanium(IV)isopropoxide 、 sodium hydride 作用下， 以 四氢呋喃 、 二氯甲烷 、 mineral oil 为溶剂， 反应 54.42h， 生成 (2S,3S)-2-phenyl-3-((prop-2-yn-1-yloxy)methyl)oxirane
  参考文献：
  名称：

  环氧化物的金催化活化：在双环缩酮合成中的应用

  摘要：

  介绍了金催化从环氧化物生成二醇等价物及其与 C≡C 键的分子内反应生成双环缩酮。该反应主要涉及丙酮化物的形成，其随后在金催化条件下分子内在炔烃上环化。这种方法可以扩展到制造光学纯的双环缩酮。进行氘掺入实验以确定反应机理。

  DOI：

  10.1002/ejoc.201001214

文献信息

• Towards Continuous Flow, Highly Enantioselective Allylic Amination: Ligand Design, Optimization and Supporting
  作者：Dana Popa、Rocío Marcos、Sonia Sayalero、Anton Vidal-Ferran、Miquel A. Pericàs

  DOI：10.1002/adsc.200900163

  日期：2009.7

  (‐CH2OR) has been optimized for the palladium‐catalyzed asymmetric allylic amination. The optimal catalyst (R=CH3), depicting very high catalytic activity and broad scope applicability, has been further modified to include an ω‐alkynyloxy substituent of variable length for polymer supporting via click chemistry, and has been anchored onto slightly cross‐linked azidomethyl poly(styrene). The length of a polymethylene

  对映体纯的二苯基膦基恶唑啉（PHOX）系列在其结构中包含一个空间可调的烷氧基甲基（-CH 2 OR），已针对钯催化的不对称烯丙基胺化进行了优化。表现出非常高的催化活性和广泛的适用性的最佳催化剂（R = CH 3）已被进一步修饰，以包括可变长度的ω-炔氧基取代基，以通过点击化学支持聚合物，并已锚定在稍微交联的叠氮基甲基聚（苯乙烯）上。已优化了连接PHOX单元与1,2,3-三唑连接基的多亚甲基链的长度，并以此方式制备了第一个聚合物支撑的高对映选择性烯丙基胺化的PHOX配体。已经建立了在微波促进的胺化反应中催化剂回收和再利用的条件，并且该系统最终适用于连续流操作。
• Copper-Free Intramolecular Alkyne–Azide Cycloadditions Leading to Seven-Membered Heterocycles
  作者：Míriam Sau、Carles Rodríguez-Escrich、Miquel A. Pericàs

  DOI：10.1021/ol201869y

  日期：2011.10.7

  Treatment of alk-2-ynyl derivatives of enantiopure phenylglycidol with NaN(3) triggers a cascade reaction consisting of stereospecific and regioselective epoxide ring opening followed by intramolecular azide-alkyne cycloaddition under strictly metal-free conditions. This simple one-pot procedure allows a fast buildup of molecular complexity, generating a wide array of triazolooxazepinols, triazolodiazepinols, and triazolothiazepinols.
• Gold-Catalysed Activation of Epoxides: Application in the Synthesis of Bicyclic Ketals
  作者：Rengarajan Balamurugan、Raveendra Babu Kothapalli、Ganesh Kumar Thota

  DOI：10.1002/ejoc.201001214

  日期：2011.3

  Gold-catalysed generation of diol equivalents from epoxides and their intramolecular reaction with C≡C bonds to generate bicyclic ketals is presented. This reaction essentially involves the formation of an acetonide, which subsequently cyclises on the alkyne intramolecularly under gold catalysis conditions. This method could be extended to make optically pure bicyclic ketals. Deuterium incorporation

  介绍了金催化从环氧化物生成二醇等价物及其与 C≡C 键的分子内反应生成双环缩酮。该反应主要涉及丙酮化物的形成，其随后在金催化条件下分子内在炔烃上环化。这种方法可以扩展到制造光学纯的双环缩酮。进行氘掺入实验以确定反应机理。
• A Recyclable, Immobilized Analogue of Benzotetramisole for Catalytic Enantioselective Domino Michael Addition/Cyclization Reactions in Batch and Flow
  作者：Javier Izquierdo、Miquel A. Pericàs

  DOI：10.1021/acscatal.5b02121

  日期：2016.1.4

  A polystyrene-supported, enantiopure benzote-tramisole (BTM) analogue (5) has been synthesized from (2S,3S)-phenylglycidol through a five-step sequence involving a copper-catalyzed alkyne azide cycloaddition (CuAAC) reaction as the final, immobilization step. The functional resin 5 (f = 0.9 mmol g(-1)) has been successfully used as a highly active and enantioselective catalyst in the domino Michael addition/cyclization reaction of in situ activated arylacetic acids (7) with chalcone-type tosylimines (6), leading to dihydropyridinones 8 (17 examples) to afford the products with excellent yields and very high enantioselectivity (mean ee 97.4%). The deactivation of 5 by species present during the catalytic process has been studied, and pivaloyl chloride (required for the activation of the arylacetic acid) has been identified as the main source of deactivation. A simple experimental protocol taking this fact into account has allowed the multiple recycling of 5 with only a marginal decrease in catalytic activity and the implementation of a continuous flow process where the activation of phenylacetic acid (residence time 14.2 min), the asymmetric domino Michael addition/cydization reaction (residence time 7.5 min), and aqueous workup are performed sequentially, delivering the dihydropyridinone product as a clean dichloromethane solution (0.54 mmol catalyst sample; 11 h operation; 8a (4.44 g, >99.9% ee)). The supported catalyst 5 has also been used in a new domino Michael addition/cydization reaction involving saccharin-derived tosylimines 9 as electrophiles, leading to 8,9-dihydro-7H-benzo[4,5]isothiazolo [2,3-[a]pyridin-7-one 5,5-dioxides 10 (8 examples) in high isolated yields and diastereoselectivities and excellent enantioselectivities (mean ee 98%). A single sample of 5 (0.5 g, 0.45 mmol) has been used for the sequential preparation in batch of a library of 7 different derivatives 10 at the gram scale (ca. 10 g, accumulated TON = 51), the whole process being performed without any column chromatographic purification. The increased diastereoselectivity recorded with 5 in reactions involving sterically congested arylacetic acids (with respect to homogeneous BTM) has been rationalized through the occurrence of steric interactions between the sulfonylimine and the linker plus support catalyst fragments leading to additional destabilization of the transition state leading to the minor, cis diastereomer of products 8/10.