N-propionyl-(1S,5R,7R)-10,10-dimethyl-3-oxo-2-aza-4-oxatricyclo<5.2.1.0^1,5>decane | 137208-49-2

• 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-propionyl-(1S,5R,7R)-10,10-dimethyl-3-oxo-2-aza-4-oxatricyclo<5.2.1.0^1,5>decane
• 英文别名: N-propionyl-(1S,5R,7R)-10,10-dimethyl-3-oxy-2-aza-4-oxatricyclo<6.2.1.0^1,5>decane；(1S,5R,7R)-10,10-dimethyl-2-propanoyl-4-oxa-2-azatricyclo[5.2.1.01,5]decan-3-one
• CAS: 137208-49-2
• 化学式: C₁₃H₁₉NO₃
• 分子量: 237.299
• InChiKey: QWRXNVVFSJOBCS-JRKPZEMJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  苯甲醛 、 N-propionyl-(1S,5R,7R)-10,10-dimethyl-3-oxo-2-aza-4-oxatricyclo<5.2.1.0^1,5>decane 在 三氟甲磺酸二丁硼 、 双氧水 、 N,N-二异丙基乙胺 作用下， 生成 N-<(2S,3S)-3-hydroxy-2-methyl-3-phenylpropionyl>-(1S,5R,7R)-10,10-dimethyl-3-oxo-2-aza-4-oxatricyclo<5.2.1.0^1,5>decane
  参考文献：
  名称：

  A superior chiral auxiliary in aldol condensation: camphor-based oxazolidone

  摘要：

  The aldol reactions from boron enolate derived from camphor-based N-propionyloxazolidone exhibit exceptionally high stereoselection. The initial aldol adducts from lithium mediated reactions equilibrate to furnish erythro isomers. Erythro selection is controlled by the choice of the enolate counterion.

  DOI：

  10.1016/0040-4039(91)80084-j
• 作为产物：
  描述：

  (S)-(+)-酮基蒎酸 在 sodium tetrahydroborate 、 sodium azide 、 cerium(III) chloride 、 氯甲酸乙酯 、 sodium hydride 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 生成 N-propionyl-(1S,5R,7R)-10,10-dimethyl-3-oxo-2-aza-4-oxatricyclo<5.2.1.0^1,5>decane
  参考文献：
  名称：

  樟脑酰亚胺烯醇化物的不对称烷基化反应

  摘要：

  衍生自樟脑的恶唑烷酮的螯合锂的酰亚胺烯醇化物与各种烷基卤化物的烷基化为烷基化产物提供了良好或优异的非对映选择性。

  DOI：

  10.1016/s0040-4039(00)93507-x

文献信息

• A superior chiral auxiliary in aldol condensation: camphor-based oxazolidone
  作者：Tu-Hsin Yan、Vir-Vir Chu、Ta-Chin Lin、Woei-Hung Tseng、Tun-Wen Cheng

  DOI：10.1016/0040-4039(91)80084-j

  日期：1991.9

  The aldol reactions from boron enolate derived from camphor-based N-propionyloxazolidone exhibit exceptionally high stereoselection. The initial aldol adducts from lithium mediated reactions equilibrate to furnish erythro isomers. Erythro selection is controlled by the choice of the enolate counterion.
• A General, Highly Anti-Stereoselective Aldolization Method via Camphor-Derived Boryl Enolates
  作者：Ying-Chuan Wang、An-Wei Hung、Chii-Shin Chang、Tu-Hsin Yan

  DOI：10.1021/jo9520147

  日期：1996.1.1

  Camphor-derived chiral boryl enolates are highly reactive and highly anti-stereoselective enolate synthon systems in aldol addition reactions promoted by a TiCl4 or SnCl4 cocatalyst. More significantly, this high-yield reaction exhibits remarkable generality with respect to the aldehyde nature, as illustrated by the rapid and anti-stereoselective aldolizations with the simple saturated and unsaturated aliphatic aldehydes, and aromatic aldehydes at temperatures as low as -90 degrees C. The enhanced reaction generality and anti stereoselectivity of camphor-derived boryl enolates suggests the importance of the nature of chiral auxiliary architecture in determining the aldol bond construction process. Final nondestructive camphor-based auxiliary removal via hydroperoxide-mediated hydrolysis affords enantiomerically pure anti-beta-hydroxy-alpha-methyl aldol products.
• Asymmetric alkylation reactions of camphor-based imide enolate
  作者：Tu-Hsin Yan、Vir-Vir Chu、Ta-Chin Lin、Chih-Hung Wu、Ling-Hsiang Liu

  DOI：10.1016/s0040-4039(00)93507-x

  日期：1991.9

  Alkylations of lithium-chelated imide enolate derived from camphor-based oxazolidone with a variety of alkyl halides provide alkylated products with good to excellent diastereoselectivity.

  衍生自樟脑的恶唑烷酮的螯合锂的酰亚胺烯醇化物与各种烷基卤化物的烷基化为烷基化产物提供了良好或优异的非对映选择性。
• Asymmetric aldol reactions: a novel model for switching between chelation- and non-chelation-controlled aldol reactions
  作者：Tu Hsin Yan、Chang Wei Tan、Hui Chun Lee、Hua Chi Lo、Tzung Yu Huang

  DOI：10.1021/ja00060a010

  日期：1993.4

  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.