(1R,2R)-1a,2,3,7b-tetrahydronaphth[1,2-b]oxirene

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 英文名称: (1R,2R)-1a,2,3,7b-tetrahydronaphth[1,2-b]oxirene
• 英文别名: 1,2-dihydronaphthalene epoxide；(1aR,7bR)-1a,2,3,7b-tetrahydronaphtho[1,2-b]oxirene
• 化学式: C₁₀H₁₀O
• 分子量: 146.189
• InChiKey: ZWBOIOUXXAJRAU-NXEZZACHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1R,2R)-1a,2,3,7b-tetrahydronaphth[1,2-b]oxirene 在 正丁基锂 、 1,10-菲罗啉 作用下， 以 正己烷 为溶剂， 反应 45.33h， 生成 (1R,2S)-1-(4-氯-3-甲氧基苯基)-N-(2,2-二甲氧基乙基)-N-甲基-1,2,3,4-四氢萘-2-胺
  参考文献：
  名称：

  Novel Stereoselective Syntheses of the Fused Benzazepine Dopamine D₁ Antagonist (6aS,13bR)-11-Chloro-6,6a,7,8,9,13b-hexahydro-7-methyl-5H- benzo[d]naphth[2,1-b]azepin-12-ol (Sch 39166):  1. Aziridinium Salt Based Syntheses

  摘要：

  Several novel enantioselective syntheses of the dopamine D-1 antagonist (6aS,13bR)-11-chloro-6,6a,7,8,9,13b-hexahydro-7- methyl-5H-benzo[d]naphth[2,1-b]azepin-12-ol (2) are described in which the key intermediate was 1-(2,2 dimethoxyethyl)-1-methyl-1a,2,3,7b-tetrahydro-1H-naphth[1,2-b] aziridinium salt (20), The latter species was prepared either from 1-(2,2-dimethoxyethyl)-1a,2,3,7b-tetrahydro-]H-naphth[1,2-b]- azirine (18) by methylation or from the tertiary amino alcohols 1-[(2,2-dimethoxyethyl)methylamino]-1,2,3,4-tetrahydro-2 -naphthalenol (23) or 2-[(2,2-dimethoxyethyl)methylamino]-1,2,3,4-tetrahydro -1-naphthalenol (24) by tosylation and in situ ring closure. Regioselective trapping of 20 with Grignard reagent (4-chloro-3-methoxyphenyl)magnesium bromide (10) then afforded the transamine 1-(4-chloro-3-methoxyphenyl)-N-(2,2-dimethoxyethyl)-1,2,3,4 -tetrahydro-N-methyl-2-naphth-alenamine (22), which was cyclized to give 11-chloro-6,6a,7,8,9,13b-hexahydro-7-methyl-12-methoxy-5H-benzo [d]- naphth[2,1-b]azepine (9), a known precursor of 2, Several enantioselective syntheses, including a Jacobsen epoxidation route, a de novo synthesis from L-homophenylalanine, and a classical salt resolution sequence, were developed for the preparation of the key intermediates in chiral form.

  DOI：

  10.1021/op970121s
• 作为产物：
  描述：

  1,2-二氢萘 在 citrate buffer 、 双氧水 作用下， 以 丙酮 为溶剂， 反应 2.0h， 以85%的产率得到(1R,2R)-1a,2,3,7b-tetrahydronaphth[1,2-b]oxirene
  参考文献：
  名称：

  Highly enantioselective epoxidation of disubstituted alkenes with hydrogen peroxide catalyzed by chloroperoxidase

  摘要：

  DOI：

  10.1021/ja00063a091

文献信息

• Chiral salen Cr(<scp>iii</scp>) complexes encapsulated in thermo-responsive polymer nanoreactors for asymmetric epoxidation of alkenes in water
  作者：Weiying Wang、Chaoping Li、Yibing Pi、Jiajun Wang、Rong Tan、Donghong Yin

  DOI：10.1039/c9cy01398a

  日期：——

  behaving as a quasi-homogeneous catalyst for the aqueous asymmetric epoxidation. Second, they effectively sequestered substrates from the surrounding environment, creating a highly concentrated environment for efficient catalysis. Third, water was excluded from the nanoreactor, minimizing the undesired hydrolysis of epoxides. As a result, the compartmentalized catalysts mediated aqueous asymmetric epoxidation

  手性Salen铬（III）（铬（沙仑））复合物通过折叠聚的两亲性无规共聚物（封装在热敏性聚合物纳米反应器Ñ -isopropylacrylamide-共-IL /铬（沙仑））（聚（NIPAAM-共-IL / Cr（salen））在水中的Cr（salen）附近。所得的催化纳米反应器与传统的Cr（salen）体系相比，在水中烯烃的不对称环氧化方面表现出一些优势。首先，将它们分散在水中，作为水不对称环氧化的准均相催化剂。其次，它们有效地隔离了周围环境中的底物，从而为高效催化创造了一个高度集中的环境。第三，将水从纳米反应器中排除，从而最大程度地减少了不希望的环氧化物水解。结果，间隔催化剂介导了水不对称环氧化，具有前所未有的收率（92–95％）和对映选择性（ee，92–99％），而传统的Cr（salen）催化剂的效率要低得多（4-12％的收率和29–44％ee）。而且，催化纳米反应器可通过热控分离方
• Ionic liquid-functionalized graphene oxide as an efficient support for the chiral salen Mn(<scp>iii</scp>) complex in asymmetric epoxidation of unfunctionalized olefins
  作者：Weiguo Zheng、Rong Tan、Shenfu Yin、Yaoyao Zhang、Guangwu Zhao、Yaju Chen、Donghong Yin

  DOI：10.1039/c4cy01290a

  日期：——

  oxide (GO) was prepared and used to support chiral salen Mn(III) complexes. Technologies of characterization suggested that the intact chiral complex was covalently appended on flat planes and edge of the GO sheet through an imidazolium-based IL linker. The flexible layer-structure, as well as the active role of the IL linker in overall reaction, makes the novel heterogeneous catalyst efficient and universal

  制备了基于咪唑鎓离子液体（IL）的氧化石墨烯（GO）并用于支撑手性Salen Mn（III）复合体。表征技术表明，完整的手性复合物通过基于咪唑的IL连接子共价附着在GO片的平面和边缘上。灵活的层结构以及IL接头在整个反应中的积极作用，使得这种新型的多相催化剂对于使用NaClO作为氧化剂的未官能化烯烃的对映选择性环氧化反应具有高效性和通用性。在广泛的烯烃（苯乙烯，α-甲基苯乙烯，茚，1,2-二氢萘，6-氰基-2,2-二甲基亚甲基和6-硝基）上观察到反应速率显着提高，转化率极高（99％） -2,2-二甲基色烯）。除苯乙烯（ee，40％）和α-甲基苯乙烯（ee，44％）外，环氧化物的对映体过量（ee）也令人鼓舞（73-93％）。更重要的是，
• Covalently functionalized carbon nanoparticles with a chiral Mn-Salen: a new nanocatalyst for enantioselective epoxidation of alkenes
  作者：Agatino Zammataro、Chiara Maria Antonietta Gangemi、Andrea Pappalardo、Rosa Maria Toscano、Roberta Puglisi、Giuseppe Nicotra、Maria Elena Fragalà、Nunzio Tuccitto、Giuseppe Trusso Sfrazzetto

  DOI：10.1039/c9cc01825e

  日期：——

  A new protocol to obtain carbon nanoparticles (CNPs) covalently functionalized with a chiral Mn-Salen catalyst is described here. The new nanocatalyst (CNPs-Mn-Salen) was tested in the enantioselective epoxidation of some representative alkenes (CN-chromene, 1,2-dihydronaphthalene and cis-β-ethyl styrene), obtaining better enantiomeric excess values than that of the catalyst single molecule, highlighting

  本文介绍了一种获得手性Mn-Salen催化剂共价官能化的碳纳米颗粒（CNP）的新方案。在某些代表性烯烃（CN-色烯，1,2-二氢萘和顺-β-乙基苯乙烯）的对映选择性环氧化反应中测试了新型纳米催化剂（CNPs-Mn-Salen），其对映体过量值优于单一催化剂。分子，突出了纳米结构在对映选择性中的作用。
• Highly enantioselective epoxidation of disubstituted alkenes with hydrogen peroxide catalyzed by chloroperoxidase
  作者：Eric J. Allain、Lowell P. Hager、Li Deng、Eric N. Jacobsen

  DOI：10.1021/ja00063a091

  日期：1993.5
• Novel Stereoselective Syntheses of the Fused Benzazepine Dopamine D₁ Antagonist (6a<i>S</i>,13b<i>R</i>)-11-Chloro-6,6a,7,8,9,13b-hexahydro-7-methyl-5<i>H</i>- benzo[<i>d</i>]naphth[2,1-<i>b</i>]azepin-12-ol (Sch 39166):  1. Aziridinium Salt Based Syntheses
  作者：Richard W. Draper、Donald Hou、Radha Iyer、Gary M. Lee、Jimmy T. Liang、Janet L. Mas、Wanda Tormos、Eugene J. Vater、Frank Günter、Ingrid Mergelsberg、Dominik Scherer

  DOI：10.1021/op970121s

  日期：1998.5.1

  Several novel enantioselective syntheses of the dopamine D-1 antagonist (6aS,13bR)-11-chloro-6,6a,7,8,9,13b-hexahydro-7- methyl-5H-benzo[d]naphth[2,1-b]azepin-12-ol (2) are described in which the key intermediate was 1-(2,2 dimethoxyethyl)-1-methyl-1a,2,3,7b-tetrahydro-1H-naphth[1,2-b] aziridinium salt (20), The latter species was prepared either from 1-(2,2-dimethoxyethyl)-1a,2,3,7b-tetrahydro-]H-naphth[1,2-b]- azirine (18) by methylation or from the tertiary amino alcohols 1-[(2,2-dimethoxyethyl)methylamino]-1,2,3,4-tetrahydro-2 -naphthalenol (23) or 2-[(2,2-dimethoxyethyl)methylamino]-1,2,3,4-tetrahydro -1-naphthalenol (24) by tosylation and in situ ring closure. Regioselective trapping of 20 with Grignard reagent (4-chloro-3-methoxyphenyl)magnesium bromide (10) then afforded the transamine 1-(4-chloro-3-methoxyphenyl)-N-(2,2-dimethoxyethyl)-1,2,3,4 -tetrahydro-N-methyl-2-naphth-alenamine (22), which was cyclized to give 11-chloro-6,6a,7,8,9,13b-hexahydro-7-methyl-12-methoxy-5H-benzo [d]- naphth[2,1-b]azepine (9), a known precursor of 2, Several enantioselective syntheses, including a Jacobsen epoxidation route, a de novo synthesis from L-homophenylalanine, and a classical salt resolution sequence, were developed for the preparation of the key intermediates in chiral form.