(+)-(S)-4-(N,N-dibenzylamino)-5-oxopentyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate | 253882-19-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (+)-(S)-4-(N,N-dibenzylamino)-5-oxopentyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate
• 英文别名: [(4S)-4-(dibenzylamino)-5-oxopentyl] 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate
• CAS: 253882-19-8
• 化学式: C₂₇H₃₆N₂O₄
• 分子量: 452.594
• InChiKey: GBNYWYITBLUALY-DEOSSOPVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.02
• 重原子数：
  33.0
• 可旋转键数：
  10.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  59.08
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (+)-(S)-4-(N,N-dibenzylamino)-5-oxopentyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate 在 potassium tert-butylate 、 仲丁基锂 、 鹰爪豆碱 作用下， 以 乙醚 为溶剂， 反应 18.0h， 生成 (-)-(1R,2R,3S)-2[(R/S)-(deutero)(phenyl)methyl]-3-(dibenzylamino)cyclopentyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate
  参考文献：
  名称：

  (−)-Sparteine-Mediated Asymmetric Intramolecular Carbolithiation of Alkenes: Synthesis of Enantiopure Cyclopentanes with Three Consecutive Stereogenic Centers

  摘要：

  An asymmetric intramolecular carbolithiation reaction was developed by combining the (-)-sparteine-mediated enantiotopos-differentiating deprotonation and the anionic 5-exo-trig cyclization. Achiral 6-phenyl-hex-5-enyl carbamates were efficiently cyclized furnishing regio-, diastereo- (dr > 99:1),and enantioselectively (er >98:2) 1,2-trans-substituted cyclopentanes. The intermediate primary benzylic Lithium-carbanion pairs were - in spite of their configurative lability - diastereoselectively substituted by versatile electrophiles creating a third consecutive stereogenic center. Additionally, some 4-functionalized 6-phenylhex-5-enyl carbamates were also cyclized in high yield to provide enantiomericaliy pure cyclopentanes incorporating three adjacent stereogenic centers.

  DOI：

  10.1002/(sici)1522-2675(19991110)82:11<1860::aid-hlca1860>3.0.co;2-8
• 作为产物：
  描述：

  (-)-(S)-4-(N,N-dibenzylamino)-5-(triphenylmethoxy)-1-pentyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate 在 草酰氯 、 二甲基亚砜 、 三乙胺 、 三氟乙酸 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 0.5h， 生成 (+)-(S)-4-(N,N-dibenzylamino)-5-oxopentyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate
  参考文献：
  名称：

  (−)-Sparteine-Mediated Stereoselective Intramolecular Carbolithiation of 4-Substituted 5-Hexynyl Carbamates. Synthesis of Enantiopure 1,3-Difunctionalized Alkylidene Cyclopentanes

  摘要：

  The stereoselective carbolithiation of alkynes with external chiral induction has been achieved for the first time by fusing the concepts of the asymmetric deprotonation (A) with s-BuLi/(-)-sparteine (s-BuLi/1) and the intramolecular carbolithiation (B). Several 4-functionalized 5-hexynyl carbamates with different terminal substituents have been prepared and efficiently cyclized providing enantiopure highly substituted alkylidene cyclopentanes. The presence of a sterically demanding substituent in the propargylic position is the essential feature of these cyclizations in order to suppress the abstraction of the remaining propargylic proton. Furthermore, in dependence on the terminal substituent, the 6-phenyl-substituted precursors undergo an intramolecular carbolithiation whereas for the 6-trimethylsilyl-substituted alkynes a sub sequent migration of the O-carbamoyl group onto the vinylic carbanionic center follows.

  DOI：

  10.1021/jo991095u