(+)-(E,S)-N-methyl-S-(3-cyclohexyl-2-propenyl)-S-phenylsulfoximine | 329770-66-3

• 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: (+)-(E,S)-N-methyl-S-(3-cyclohexyl-2-propenyl)-S-phenylsulfoximine
• 英文别名: (+)-(E,S)-3-cyclohexyl-1-(N-methyl-S-phenylsulfonimidoyl)-prop-2-ene；[(E)-3-cyclohexylprop-2-enyl]-methylimino-oxo-phenyl-lambda6-sulfane；[(E)-3-cyclohexylprop-2-enyl]-methylimino-oxo-phenyl-λ6-sulfane
• CAS: 329770-66-3
• 化学式: C₁₆H₂₃NOS
• 分子量: 277.431
• InChiKey: MHFQKHKKERFOJH-BLRBJFNZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  37.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+)-(E,S)-N-methyl-S-(3-cyclohexyl-2-propenyl)-S-phenylsulfoximine 在 正丁基锂 、 trimethoxonium tetrafluoroborate 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 生成 (+)-(S)-N,N-dimethyl benzenesulfinamide
  参考文献：
  名称：

  Functionalized Chiral Vinyl Aminosulfoxonium Salts:  Asymmetric Synthesis and Application to the Synthesis of Enantiopure Unsaturated Prolines, β,γ-Dehydro Amino Acids, and Cyclopentanoid Keto Aminosulfoxonium Ylides

  摘要：

  Methylation of the enantiopure functionalized vinyl sulfoximines 5a-e and 14a-d followed by a F-ion or DBU-mediated isomerization of the vinyl aminosulfoxonium salts 7a-e and 15a-d, respectively, gave the allyl aminosulfoxonium salts 10a-e and 17a-d, respectively. A concomitant intramolecular substitution of the aminosulfoxonium group of 10a-e and 17a-d by the amino group afforded the unsaturated prolines 8a-e and 18a-d, respectively. The starting vinyl sulfoximines are accessible through a highly selective and stereo-complementary aminoalkylation of the corresponding sulfonimidoyl-substituted mono- and bis( allyl) titanium complexes with the imino ester 4. The vinyl aminosulfoxonium salts 34, 7a-d, and E-15c experienced upon treatment with the Cl- ion a migratory substitution with formation of the delta-chloro-beta,gamma-dehydro amino acids 36, E/Z-37a-d, and 38, respectively. A migratory substitution of the hydroxy-substituted vinyl aminosulfoxonium salts 46a and 46b furnished the delta-chloro allyl alcohols E/Z-48a and E-48b, respectively. A facile one-pot conversion of the vinyl sulfoximines 31b, 5c and 45a to the allyl chlorides 36, E/Z-37c and E/Z-48a, respectively, was achieved upon treatment with a chloroformiate. A tandem cyclization of the vinyl aminosulfoxonium salts 7b, Al-7b and 57 with LiN( H) tBu yielded the cyclopentanoid keto aminosulfoxonium ylides 54, Al-54, 59, 60 and 61, respectively. The structure of the tricyclic keto aminosulfoxonium ylide Al-54 has been determined by X-ray crystal structure analysis. Ab initio calculations and a NBO analysis of the tricyclic keto aminosulfoxonium ylide XXIII show a polar structure stabilized by electrostatic interactions between the ylidic C atom and both the carbonyl C atom and the S atom.

  DOI：

  10.1021/ja061152i
• 作为产物：
  描述：

  N,S-dimethyl-S-phenylsulfoximine 在 正丁基锂 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 正己烷 、 乙腈 为溶剂， 反应 38.0h， 生成 (+)-(E,S)-N-methyl-S-(3-cyclohexyl-2-propenyl)-S-phenylsulfoximine
  参考文献：
  名称：

  N-甲基磺酰亚胺酰基取代的（2-烯基）钛配合物：在β-和δ-磺酰亚胺酰基取代的手性高烯丙醇合成中的应用、X 射线晶体结构分析和通量行为

  摘要：

  已从 N,S-二甲基-S-苯基亚砜亚胺和醛通过加成-消除-异构化路线通过相应的 (E)-构型乙烯基亚砜的中间生成合成了对映体纯无环 (E)-和 (Z)-构型的烯丙基亚砜亚胺亚砜亚胺。乙烯基亚砜亚胺与 DBU 的异构化优先提供相应的 (Z)-构型的烯丙基亚砜亚胺，随后由 DBU 异构化以优先产生 (E)-异构体。用 ClTi(OiPr)3 对锂化 (E)-构型的烯丙基亚砜亚胺进行钛化，得到相应的双（2-烯基）二异丙氧基钛（IV）配合物，其在 ClTi(OiPr)3 存在下与醛反应，在 γ 位具有高区域选择性和非对映选择性，以良好的产率得到相应的 (Z)-反构型 δ-N-甲基磺酰亚胺酰基取代的高烯丙醇。在低温下不存在 ClTi(OiPr)3 的情况下，只有双（烯基）二异丙氧基钛络合物的一个烯丙基部分转移到醛上。通过这种方式，环状锂化烯丙基亚砜亚胺以高区域选择性和非对映选择性转化为相应的带有乙烯基磺酰亚胺酰基的高烯丙醇。用

  DOI：

  10.1002/1099-0690(200012)2000:24<3973::aid-ejoc3973>3.0.co;2-b

文献信息

• Asymmetric Synthesis of Highly Substituted γ-Amino Acids from Allyltitanium Sulfoximines
  作者：Franz Köhler、Hans-Joachim Gais、Gerhard Raabe

  DOI：10.1021/ol063082q

  日期：2007.3.1

  [structure: see text]. Asymmetric syntheses of the highly substituted protected gamma-amino acids 10a, 10b, 18, and 21 have been developed starting from the allyltitanium sulfoximines V and VI, respectively, and furan-2-carbaldehyde.

  [结构：见文字]。已经分别从烯丙基钛亚砜肟亚胺V和VI以及呋喃-2-甲醛开始发展了高度取代的受保护的γ-氨基酸10a，10b，18和21的不对称合成。
• Asymmetric aziridination with chiral allyl aminosulfoxonium ylides: synthesis of alkenyl aziridine carboxylates and palladium-catalyzed E,trans/E,cis-isomerization of an alkenyl aziridine
  作者：Vijaya Bhaskara Reddy Iska、Hans-Joachim Gais、Shashi Kant Tiwari、Gadamsetti Surendra Babu、Adeline Adrien

  DOI：10.1016/j.tetlet.2007.07.216

  日期：2007.10

  Chiral cyclic and acyclic allyl aminosulfoxonium ylides have been generated from aminosulfoxonium-substituted β,γ-unsaturated α-amino acids (method A) and 1-alkenyl aminosulfoxonium salts (method B) upon treatment with DBU. Their application to the asymmetric aziridination of N-tert-butyl-sulfonyl imino ester, generated either in situ (method A) or externally added (method B), gave the corresponding

  在用DBU处理后，由氨基s取代的β，γ-不饱和α-氨基酸（方法A）和1-烯基氨基s生成的盐（方法B）已生成手性环状和无环烯丙基氨基ulf氧化物。其应用到的不对称氮杂环丙烷Ñ -叔丁基-磺酰亚氨基酯，原位（方法A）或外部添加（方法B）或者生成，得到相应的链烯基的氮丙啶羧酸盐与中到高非对映选择性和对映选择性。描述了E，反式构型的烯基氮丙啶甲醇衍生物到其E-顺式异构体的高度立体选择性Pd（0）-催化的异构化，其继续保持双键构型。
• Asymmetric Synthesis of Fused Bicyclic α-Amino Acids Having a Hexahydro-cyclopenta[<i>c</i>]pyridine Skeleton via Intramolecular Pauson−Khand Reaction of 1-Sulfonimidoyl-Substituted 5-Azaoct-1-en-7-ynes
  作者：Markus Günter、Hans-Joachim Gais

  DOI：10.1021/jo030171x

  日期：2003.10.1

  An asymmetric synthesis of fused bicyclic amino acids having a hexahydro-cyclopenta[c]pyridine skeleton and carrying besides an enone structural element a substituent at the beta-position is described. The key steps of the synthesis are a highly selective allylation of N-tert-butylsulfonyl imino ester with bis(allylsulfoximine)titanium complexes and a highly diastereoselective Pauson-Khand cycloaddition of sulfonimidoyl-substituted gamma,delta-unsaturated alpha-amino acid esters carrying a substituent at the beta-position and a propargyl group at the N-atom. The cyclization is accompanied by a reductive cleavage of the sulfoximine group of the primary cyclization product. Surprisingly, the removal of the sulfoximine group proceeds with inversion of the configuration at the S-atom and gives N-methyl-phenylsulfinamide with greater than or equal to98% ee. Deprotection of the bicyclic N-tert-butylsulfonyl-protected amino acid ester was accomplished through treatment with CF3SO3H under anhydrous conditions. The enantio- and diastereomerically pure sulfoximine-substituted gamma,delta-unsaturated alpha-amino acid esters used as starting material were obtained through a highly regio- and diastereoselective allylation of N-tert-butylsulfonyl imino ester with acyclic bis(allylsulfoximine)titanium complexes, described previously.