(1R,2S)-N-methylephedrine | 46864-14-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: (1R,2S)-N-methylephedrine
• 英文别名: (1R,2S)-2-N,N-dimethylamino-1,2-diphenyl ethanol；(-)-erythro-2-dimethylamino-1,2-diphenylethanol；(1R,2S)-N,N-dimethyl-2-amino-1,2-diphenyl ethanol；(1S,2R)-N,N-dimethyl-2-hydroxy-1,2-diphenyl-ethylamine；(1R,2S)-2-dimethylamino-1,2-diphenylethanol；(1R,2S)-2-(dimethylamino)-1,2-diphenylethanol
• CAS: 46864-14-6
• 化学式: C₁₆H₁₉NO
• 分子量: 241.333
• InChiKey: MLJRRPFUCGOHPB-JKSUJKDBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  23.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R,2S)-N-methylephedrine 在 四氯化钛 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 (2R,3R)-3-Hydroxy-2-methyl-octanoic acid (1R,2S)-2-dimethylamino-1,2-diphenyl-ethyl ester
  参考文献：
  名称：

  Enantioselective synthesis of anti-.alpha.-methyl-.beta.-hydroxy esters through titanium tetrachloride-mediated aldol condensation

  摘要：

  DOI：

  10.1021/ja00306a045
• 作为产物：
  描述：

  (1R,2S)-2-氨基-1,2-二苯基乙醇 在 sodium tetrahydroborate 作用下， 以 乙醇 为溶剂， 反应 12.5h， 生成 (1R,2S)-N-methylephedrine
  参考文献：
  名称：

  Easily accessible chiral amino-phosphinite ligands for highly enantioselective palladium-mediated allylic alkylation

  摘要：

  Palladium-catalyzed asymmetric allylic alkylation of 1,3-diplienyl-2-propenyl acetate with the dimethyl malonate-BSA-LiOAc system has been successfully carried out in the presence of easily prepared new chiral amino-phosphinite ligands such as 3b and 3c to result in good yields and excellent enantioselectivities of up to 95%, e.e. (C) 2002 Published by Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(02)00204-5
• 作为试剂：
  描述：

  重氮乙酸乙酯 、 苯甲醛 在 Dimethylzinc 、 (1R,2S)-N-methylephedrine 作用下， 以 乙醚 为溶剂， 反应 24.0h， 生成 ethyl 2-diazo-3-phenyl-3-hydroxypropanoate
  参考文献：
  名称：

  重氮乙酸乙酯对酮类的第一个催化对映选择性羟醛型反应

  摘要：

  酮中的醛醇型加成仍然代表着不对称催化的巨大挑战。近来，可商购的重氮乙酸乙酯和醛之间的直接醇醛反应已引起越来越多的关注。重氮乙酸乙酯是经济的，并且可以使所获得的羟醛加合物进一步转化。我们提出了将重氮基乙酸酯加到酮上的艰苦而未曾描述的解决方案。我们的程序使用了市售的去甲麻黄碱衍生的配体和二烷基锌试剂[R 2 Zn：（二乙基锌，Et 2 Zn;二甲基锌，Me 2（Zn）]作为起始原料，因此用非常简单的方法制备活性催化剂。显着地，该反应与α-卤代酮产生了良好的对映体过量，α-卤代酮是烯醇化物添加中不常用的一类化合物。

  DOI：

  10.1002/adsc.200900435

文献信息

• Synthesis and Reactivities of Enantiomerically Pure β-Hydroxyalkyl and β-Aminoalkyl Ferrocenyl Sulfides
  作者：Luca Bernardi、Bianca F. Bonini、Mauro Comes-Franchini、Mariafrancesca Fochi、Germana Mazzanti、Alfredo Ricci、Greta Varchi

  DOI：10.1002/1099-0690(200208)2002:16<2776::aid-ejoc2776>3.0.co;2-y

  日期：2002.8

  Enantiomerically pure β-hydroxyalkyl and β-aminoalkyl ferrocenyl sulfides have been synthesized in good yields from mercaptoferrocene and amino alcohol derivatives. Primary β-aminoalkyl sulfides allowed the synthesis of tetrahydro-1,4-thiazepines containing the ferrocene moiety with good diastereoselectivity and β-iminoalkyl sulfides. Some of these derivatives have successfully been employed as ligands

  已经从巯基二茂铁和氨基醇衍生物以良好的产率合成了对映体纯的 β-羟烷基和 β-氨基烷基二茂铁基硫化物。伯 β-氨基烷基硫化物允许​​合成含有具有良好非对映选择性的二茂铁部分和 β-亚氨基烷基硫化物的四氢-1,4-硫氮杂。其中一些衍生物已成功用作钯催化烯丙基取代的配体，不对称诱导高达 99% ee。(© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)
• Optical Resolution of 2-Amino-1,2-diphenylethanol by Preferential Crystallization and Its Utilization in Fractional Crystallization and Enantioselective Reduction of Prochiral Ketones
  作者：Kazuhiko Saigo、Shigeo Ogawa、Shigetoshi Kikuchi、Atsushi Kasahara、Hiroyuki Nohira

  DOI：10.1246/bcsj.55.1568

  日期：1982.5

  3-endo-benzamido-5-norbornene-2-endo-carboxylic acid. Chiral hydrides prepared from lithium aluminium hydride and optically active threo- or erythro-2-amino-1,2-diphenylethanol derivatives were applied to the enantioface differentiating reduction of prochiral ketones to give the corresponding optically active alcohols in 26–72% optical purities.

  由安息香肟通过催化还原制备的 (±)-erythro-2-Amino-1,2-diphenylethanol 通过优先结晶成功分解为一对旋光形式。发现旋光氨基醇可用作碱性拆分剂，用于旋光拆分酒石酸、反式-2,3-环氧乙烷二甲酸、2-羟基-2-苯基丙酸和 3-endo-benzamido-5-降冰片烯-2-内-羧酸。由氢化铝锂和旋光性苏式-或赤式-2-氨基-1,2-二苯基乙醇衍生物制备的手性氢化物应用于前手性酮的对映面差异化还原，得到相应的旋光醇，其光学纯度为 26-72%。
• Pyrrolidine derivatives and method of synthesizing these
  申请人：——

  公开号：US20040236118A1

  公开（公告）日：2004-11-25

  The object of the invention is to provide a process for efficient, inexpensive and stereoselective production of (2S,4S)-2-[[(3R)-pyrrolidin-3-yl-(R)-hydroxylmethyl]pyrrolidin-4-thiol dihydrochloride useful as an intermediate in production of novel carbapenem, and the intermediate is produced via a novel crystallizable intermediate (2S,4R)—N-t-butoxycarbonyl-2-[[(3R)—N-t-butoxycarbonyl pyrrolidin-3-yl-(R)-hydroxylmethyl]-4-hydroxypyrrolidine from a (2S,4R)-4-alkylsilyloxy-N-t-butoxycarbonylpyridine-2-carbaldehyde derivative by aldol reaction using an asymmetric assistant such as amino-alcohol.

  本发明的目的是提供一种高效、廉价和立体选择性生产(2S,4S)-2-[[(3R)-吡咯啉-3-基-(R)-羟甲基]吡咯啉-4-硫醇二盐酸盐的方法，该方法是通过使用一种新的可结晶中间体(2S,4R)-N-叔丁氧羰基-2-[[(3R)-N-叔丁氧羰基吡咯啉-3-基-(R)-羟甲基]-4-羟基吡咯烷通过使用氨基醇等不对称助剂的醛缩反应从(2S,4R)-4-烷基硅氧基-N-叔丁氧羰基吡啶-2-甲醛衍生物中制备的，该中间体可用作新型头孢菌素的中间体。
• PYRROLIDINE DERIVATIVES AND METHOD OF SYNTHESIZING THESE
  申请人：Eizai Co., Ltd.

  公开号：EP1413574A1

  公开（公告）日：2004-04-28

  The object of the invention is to provide a process for efficient, inexpensive and stereoselective production of (2S,4S)-2-[[(3R)-pyrrolidin-3-yl-(R)-hydroxy] methyl] pyrrolidin-4-thiol dihydrochloride useful as an intermediate in production of novel carbapenem, and the intermediate is produced via a novel crystallizable intermediate (2S,4R)-N-t-butoxycarbonyl-2-[[(3R)-N-t-butoxycarbonyl pyrrolidin-3-yl-(R)-hydroxy]methyl]-4-hydroxypyrrolidine from a (2S,4R)-4-alkylsilyloxy-N-t-butoxycarbonylpyridine-2-carbal dehyde derivative by aldol reaction using an asymmetric assistant such as amino-alcohol.

  本发明的目的是提供一种高效、廉价和立体选择性生产(2S,4S)-2-[[(3R)-吡咯烷-3-基-(R)-羟基]甲基]吡咯烷-4-硫醇二盐酸盐的工艺，该工艺可作为生产新型碳青霉烯的中间体、该中间体通过新型可结晶中间体(2S,4R)-N-叔丁氧羰基-2-[[(3R)-N-叔丁氧羰基吡咯烷-3-基-(R)-羟基]甲基]-4-羟基吡咯烷由(2S,4R)-4-烷基硅氧基-N-叔丁氧羰基吡啶-2-甲醛衍生物通过醛醇反应使用不对称助剂（如氨基醇）制得。
• New Catalysts for the Asymmetric Hydrosilylation of Ketones Discovered by Mass Spectrometry Screening
  作者：Sulan Yao、Jun-Cai Meng、Gary Siuzdak、M. G. Finn

  DOI：10.1021/jo026365e

  日期：2003.4.1

  A method for determining enantiomeric excess by mass spectrometry was employed to screen a family of chiral phosphite P,N-ligands for activity in the rhodium-catalyzed asymmetric hydro-silylation of ketones. The identification of an effective set of ligands was followed by preliminary studies of the reaction scope and mechanism. Asymmetric induction of 84-88% ee for larger-scale reactions was observed, which is close to the level of the best alternative catalysts previously discovered. The screening method was shown to be applicable to a variety of substrates without the need for special optimization.