N-(Phenyldiazoacetyl)camphorsultam | 170157-94-5

• 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-(Phenyldiazoacetyl)camphorsultam
• 英文别名: (1S)-(-)-N-phenyldiazoacetyl 2,10-camphorsultam；2-diazo-1-[(1S,5R,7R)-10,10-dimethyl-3,3-dioxo-3lambda6-thia-4-azatricyclo[5.2.1.01,5]decan-4-yl]-2-phenylethanone；2-diazo-1-[(1S,5R,7R)-10,10-dimethyl-3,3-dioxo-3λ6-thia-4-azatricyclo[5.2.1.01,5]decan-4-yl]-2-phenylethanone
• CAS: 170157-94-5
• 化学式: C₁₈H₂₁N₃O₃S
• 分子量: 359.449
• InChiKey: HCXHNTAFTGJIQM-HBUWYVDXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  25
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  64.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-methoxy-2-(2-propenylthio)benzene 、 N-(Phenyldiazoacetyl)camphorsultam 在 tetrakis(actonitrile)copper(I) hexafluorophosphate 、 (S,S)-N,N-bis(2,6-dichlorobenzylidene)cyclohexan-1,2-diamine 作用下， 以 二氯甲烷 为溶剂， 反应 10.0h， 生成 1-((1S,5R,7R)-10,10-Dimethyl-3,3-dioxo-3λ⁶-thia-4-aza-tricyclo[5.2.1.0^1,5]dec-4-yl)-2-(2-methoxy-phenylsulfanyl)-2-phenyl-pent-4-en-1-one
  参考文献：
  名称：

  通过 Cu(I) 卡宾和硫化物生成硫叶立德的高立体选择性 [2,3]-Sigmatropic 重排

  摘要：

  通过将手性樟脑 sultam 助剂和 Cu(I) 催化剂与手性或非手性二亚胺相结合的双不对称诱导方法，通过 Cu(I) 卡宾和烯丙基和炔丙基硫化物生成硫叶立德的高度立体选择性 [2,3]-σ 重排配体已被开发。

  DOI：

  10.1021/ja055021d
• 作为产物：
  描述：

  2-oxophenylacetyl chloride tosylhydrazone 、 (2R)-bornane-10,2-sultam 在 sodium hydride 作用下， 以 甲苯 、 paraffin 为溶剂， 以51%的产率得到N-(Phenyldiazoacetyl)camphorsultam
  参考文献：
  名称：

  Diastereoselectivity in the O-H Insertion Reactions of Rhodium Carbenoids Derived from Phenyldiazoacetates of Chiral Alcohols. Preparation of .alpha.-Hydroxy and .alpha.-Alkoxy Esters

  摘要：

  A series of phenyldiazoacetates 3 derived from enantiomerically pure alcohols ((-)-borneol, (+)menthol, (-)-menthol, (-)-8-phenylmenthol, (-)-trans-2-phenylcyclohexanol, (+)-trans-2-phenyl-cyclohexanol, and (-)10-(dicyclohexylsulfamoyl)-D-isoborneol) were prepared from the corresponding alpha-keto esters 1 by way of the tosylhydrazones 2. Rhodium(II)-catalyzed decomposition of the diazoacetates 3 in the presence of water or alcohols resulted in carbenoid O-H insertion reactions to give the corresponding 2-hydroxy- or 2-alkoxyphenylacetates in good yield, but with varying degrees of diastereoselectivity. A range of rhodium(II) and other metal catalysts were investigated, with rhodium(II) acetate and rhodium(II) acetamide giving the best results. The stereochemistry of the major diastereomer was proved in most cases by independent synthesis from a mandelic acid derivative of known configuration. Possible mechanisms are discussed.

  DOI：

  10.1021/jo00119a023

文献信息

• Catalytic Asymmetric [2,3]-Sigmatropic Rearrangement of Sulfur Ylides Generated from Copper(I) Carbenoids and Allyl Sulfides
  作者：Xiaomei Zhang、Zhaohui Qu、Zhihua Ma、Weifeng Shi、Xianglin Jin、Jianbo Wang

  DOI：10.1021/jo025687f

  日期：2002.8.1

  Catalytic asymmetric sulfur ylide [2,3]-sigmatropic rearrangement of carbenoids generated from aryldiazoacetates has been investigated with a number of chiral Rh(II) and Cu(I) catalysts, and moderately high enantioselectivity (52-78% ee) can be achieved with Cu(MeCN)(4)PF(6)/2,2'-isopropylidenebis[(4S)-4-tert-butyl-2-oxazoline].

  已经研究了使用多种手性Rh（II）和Cu（I）催化剂对由芳基重氮乙酸酯生成的类胡萝卜素进行催化的不对称丁二酸硫[2,3]-σ重排的现象，可以实现中等程度的高对映选择性（52-78％ee）与Cu（MeCN）（4）PF（6）/ 2,2'-亚丙基双[（4S）-4-叔丁基-2-恶唑啉]。
• Diastereoselective intermolecular OH insertions by Cu(II)-mediated carbenoids derived from phenyldiazoacetamide
  作者：Nan Jiang、Jianbo Wang、Albert S.C Chan

  DOI：10.1016/s0040-4039(01)01832-9

  日期：2001.11

  The diastereoselective insertion into carboxylic OH bonds was investigated with camphorsultam as a chiral auxiliary, and moderate to good selectivity was achieved.

  以樟脑为手性助剂，研究了非对映选择性插入羧基OH键中的选择性，并获得了中度至良好的选择性。
• Diastereoselectivity in the O-H Insertion Reactions of Rhodium Carbenoids Derived from Phenyldiazoacetates of Chiral Alcohols. Preparation of .alpha.-Hydroxy and .alpha.-Alkoxy Esters
  作者：Enrique Aller、David S. Brown、Geoffrey G. Cox、David J. Miller、Christopher J. Moody

  DOI：10.1021/jo00119a023

  日期：1995.7

  A series of phenyldiazoacetates 3 derived from enantiomerically pure alcohols ((-)-borneol, (+)menthol, (-)-menthol, (-)-8-phenylmenthol, (-)-trans-2-phenylcyclohexanol, (+)-trans-2-phenyl-cyclohexanol, and (-)10-(dicyclohexylsulfamoyl)-D-isoborneol) were prepared from the corresponding alpha-keto esters 1 by way of the tosylhydrazones 2. Rhodium(II)-catalyzed decomposition of the diazoacetates 3 in the presence of water or alcohols resulted in carbenoid O-H insertion reactions to give the corresponding 2-hydroxy- or 2-alkoxyphenylacetates in good yield, but with varying degrees of diastereoselectivity. A range of rhodium(II) and other metal catalysts were investigated, with rhodium(II) acetate and rhodium(II) acetamide giving the best results. The stereochemistry of the major diastereomer was proved in most cases by independent synthesis from a mandelic acid derivative of known configuration. Possible mechanisms are discussed.
• Highly Stereoselective [2,3]-Sigmatropic Rearrangement of Sulfur Ylide Generated through Cu(I) Carbene and Sulfides
  作者：Ming Ma、Lingling Peng、Changkun Li、Xiu Zhang、Jianbo Wang

  DOI：10.1021/ja055021d

  日期：2005.11.1

  A highly stereoselective [2,3]-sigmatropic rearrangement of sulfur ylide generated through Cu(I) carbene and allyl and propargyl sulfides by a double asymmetric induction approach that combines a chiral camphor sultam auxiliary and Cu(I) catalyst with chiral or achiral diimine ligands has been developed.

  通过将手性樟脑 sultam 助剂和 Cu(I) 催化剂与手性或非手性二亚胺相结合的双不对称诱导方法，通过 Cu(I) 卡宾和烯丙基和炔丙基硫化物生成硫叶立德的高度立体选择性 [2,3]-σ 重排配体已被开发。