(1S,5R,7R)-10,10-dimethyl-3-thioxo-2-aza-4-oxatricyclo<5.2.1.0^1,5>decane | 147168-90-9

• 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: (1S,5R,7R)-10,10-dimethyl-3-thioxo-2-aza-4-oxatricyclo<5.2.1.0^1,5>decane
• 英文别名: (1S,5R,7R)-10,10-dimethyl-4-oxa-2-azatricyclo[5.2.1.01,5]decane-3-thione
• CAS: 147168-90-9
• 化学式: C₁₀H₁₅NOS
• 分子量: 197.301
• InChiKey: KVZVFVZCCCSAAN-BRDIYROLSA-N

物化性质

• 沸点：
  257.4±23.0 °C(Predicted)
• 密度：
  1.24±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  53.4
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1S,5R,7R)-10,10-dimethyl-3-thioxo-2-aza-4-oxatricyclo<5.2.1.0^1,5>decane 在 四氯化钛 、 sodium hydride 、 N,N-二异丙基乙胺 作用下， 反应 0.92h， 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
• 作为产物：
  描述：

  camphor isocyanate 在 sodium tetrahydroborate 、 cerium(III) chloride 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 24.17h， 生成 (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

• Asymmetric bromination-aldolization of chiral acetate titanium enolate derived from thioimide. A general approach to the synthesis of enantiopure α-bromo-β-hydroxy carboxylic acids
  作者：Ying-Chuan Wang、Dah-Wei Su、Chen-Men Lin、Hsi-Liang Tseng、Chi-Lung Li、Tu-Hsin Yan

  DOI：10.1016/s0040-4039(99)00576-6

  日期：1999.4

  Chiral acetate titanium enolate derived from thioimide efficiently effects one-step bromination-aldolization with excellent yields and exceptionally high levels of asymmetric induction in aldol additions. General base promoted oxazolidinethione deacylation provides direct access to chiral α-bromo-β-hydroxy acids.

  衍生自硫酰亚胺的手性乙酸烯醇钛酸酯可有效完成一步溴化-醛缩醛化反应，并具有优异的收率，并且在添加醛醇缩合剂时异常高的不对称诱导率。一般的碱促进的恶唑烷硫酮脱酰作用可直接获得手性α-溴-β-羟基酸。
• “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.
• An Unusual Enantioselective Aldol-Type Reaction of an Acetate Boryl Enolate Derived from a Chiral Thioimide
  作者：Tu-Hsin Yan、An-Wei Hung、Hui-Chun Lee、Chii-Shin Chang

  DOI：10.1021/jo00105a040

  日期：1994.12

  The camphor-derived N-acetyloxazolidinethione has been used to effect enantioselective aldol type reactions of the derived 9-BBN enolate with a variety of aldehydes. Mechanistically, the observed facial selectivity is best explained by a boatlike transition structure.
• Yan, Tu-Hsin; Hung, An-Wei; Lee, Hui-Chun, Journal of the Chinese Chemical Society, 1995, vol. 42, # 4, p. 691 - 700
  作者：Yan, Tu-Hsin、Hung, An-Wei、Lee, Hui-Chun、Liu, Wen-Hung、Chang, Chii-Shin

  DOI：——

  日期：——
• Asymmetric Aldol Type Reactions of Acetate Imide Enolates
  作者：Tu-Hsin Yan、An-Wei Hung、Hui-Chun Lee、Chii-Shin Chang、Wen-Hung Liu

  DOI：10.1021/jo00116a011

  日期：1995.6

  Titanium-mediated chelation-controlled aldol type reactions of acetate thioimide enolates with representative aldehydes proceed with high ct-facial differentiation. An investigation of the influence of the nature of the imide enolate ligands and the Lewis acids in the non-chelation-controlled aldol bond construction process of acetate imide enolates reveals that alternation of either the boryl geometry or imide enolate ligand leads to pi-facial selectivity switch.