(-)-(4S,5E/Z)-4-(dibenzylamino)-6-phenylhex-5-enyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate | 205067-99-8

• 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: (-)-(4S,5E/Z)-4-(dibenzylamino)-6-phenylhex-5-enyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate
• CAS: 205067-99-8
• 化学式: C₃₄H₄₂N₂O₃
• 分子量: 526.719
• InChiKey: JLRCDNBLSACYNR-HKBQPEDESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.53
• 重原子数：
  39.0
• 可旋转键数：
  11.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  42.01
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (-)-(4S,5E/Z)-4-(dibenzylamino)-6-phenylhex-5-enyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate 在 仲丁基锂 、 鹰爪豆碱 、 氘代甲醇-d 作用下， 以 乙醚 为溶剂， 反应 18.0h， 以70%的产率得到(-)-(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：

  三苯基苄基溴化膦 、 (+)-(S)-4-(N,N-dibenzylamino)-5-oxopentyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate 在 potassium tert-butylate 作用下， 以 乙醚 为溶剂， 以80%的产率得到(-)-(4S,5E/Z)-4-(dibenzylamino)-6-phenylhex-5-enyl 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

文献信息

• (−)-Sparteine-mediated stereoselective intramolecular carbolithiation of alkynes
  作者：Martin Oestreich、Roland Fröhlich、Dieter Hoppe

  DOI：10.1016/s0040-4039(98)00085-9

  日期：1998.3

  The asymmetric deprotonation mediated by the chiral base s-butyllithium/(−)-sparteine of 4-substituted 5-hexynyl carbamates permits the synthesis of enantioenriched carbanionic pairs which undergo a regioselective 5-exo-dig ring closure with the triple bond acting as an internal electrophile. The functionalized five-membered rings are formed with complete stereoselectivity in high yields.

  由4-取代的5-己炔基氨基甲酸酯的手性碱基s-丁基锂/（-）-天冬氨酸介导的不对称去质子化反应，可以合成对映体富集的碳负离子对，该对离子通过区域选择性的5- exo - dig环封闭，其中三键充当内部亲电体。高产率地形成具有完全立体选择性的官能化五元环。