N-<(2R,3R)-3-hydroxy-2-methyl-3-phenylpropionyl>-(1S,5R,7R)-10,10-dimethyl-3-thioxo-2-aza-4-oxatricyclo<5.2.1.0^1,5>decane | 147253-91-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: N-<(2R,3R)-3-hydroxy-2-methyl-3-phenylpropionyl>-(1S,5R,7R)-10,10-dimethyl-3-thioxo-2-aza-4-oxatricyclo<5.2.1.0^1,5>decane
• 英文别名: (2R,3R)-1-[(1S,5R,7R)-10,10-dimethyl-3-sulfanylidene-4-oxa-2-azatricyclo[5.2.1.01,5]decan-2-yl]-3-hydroxy-2-methyl-3-phenylpropan-1-one
• CAS: 147253-91-6
• 化学式: C₂₀H₂₅NO₃S
• 分子量: 359.489
• InChiKey: IVFPIIZWOXPKEE-YJJXHOGASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  81.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N-<(2R,3R)-3-hydroxy-2-methyl-3-phenylpropionyl>-(1S,5R,7R)-10,10-dimethyl-3-thioxo-2-aza-4-oxatricyclo<5.2.1.0^1,5>decane 在 4-二甲氨基吡啶 、 水 作用下， 以 乙腈 为溶剂， 反应 30.0h， 以87%的产率得到(2R,3R)-(+)-3-hydroxy-2-methyl-3-phenylpropanoic acid
  参考文献：
  名称：

  DMAP-promoted racemization-free deacylation of carboxthioimide† adducts: carboxthioimide as a versatile carboxy protecting group

  摘要：

  DMAP促进的羧基硫亚胺加成物去酰化反应可以定向生成酸或各种酯保护基，且没有检测到明显的叠氢化现象。

  DOI：

  10.1039/a900577c
• 作为产物：
  描述：

  camphor isocyanate 在 sodium tetrahydroborate 、 cerium(III) chloride 、 四氯化钛 、 sodium hydride 、 三乙胺 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 25.08h， 生成 N-<(2R,3R)-3-hydroxy-2-methyl-3-phenylpropionyl>-(1S,5R,7R)-10,10-dimethyl-3-thioxo-2-aza-4-oxatricyclo<5.2.1.0^1,5>decane
  参考文献：
  名称：

  Asymmetric aldol reactions: a novel model for switching between chelation- and non-chelation-controlled aldol reactions

  摘要：

  A new camphor-based N-propionyloxazolidinethione provides remarkable levels of asymmetric induction for both chelation-and non-chelation-controlled aldol processes. While the aldol condensation of the derived di-n-butylboryl enolate with various aldehydes affords the 'Evans'' syn aldol with excellent diastereoselectivity, the chlorotitanium enolate gives the ''non-Evans' syn aldol expected from chelation control. Most noteworthy is the observation that the sense of facial selectivity from the chlorotitanium enolate of propionyloxazolidinethione is opposite to that obtained from propionyloxazolidinone. This important finding illustrates the importance of increased chelating potential of the enolate ligand, ring thiocarbonyl, in maximizing the aldol pi-facial discrimination. Final nondestructive chiral auxiliary removal via hydroperoxide-assisted hydrolysis and subsequent esterification provides enantiomerically pure methoxy-carbonyl aldols.

  DOI：

  10.1021/ja00060a010

文献信息

• “Non-Evans” syn aldol via aldolization of chlorotitanium enolate with TiCl4/aldehyde complex
  作者：Tu-Hsin Yan、Hui-Chun Lee、Chang-Wei Tan

  DOI：10.1016/s0040-4039(00)73635-5

  日期：1993.5

  Direct aldolizations of chlorotitanium enolate derived from camphor-based oxazolidinethione with 1:1 TiCl4-aldehyde complex give ''non-Evans'' syn aldol with excellent diastereoselectivity.
• A novel DMAP-promoted oxazolidinethione deacylation. Application for the direct conversion of the initial chiral thioimide aldols to various ester protecting groups
  作者：Dah-Wei Su、Ying-Chuan Wang、Tu-Hsin Yan

  DOI：10.1016/s0040-4039(99)00710-8

  日期：1999.5

  DMAP (4-(dimethylamino)pyridine) promoted nucleophilic cleavage of the initial chiral thioimide aldols can be directed to form various ester protecting groups without causing racemization of the newly created stereocenters. (C) 1999 Elsevier Science Ltd. All rights reserved.