(+)-(Z,S)-4-methyl-1-(N-methyl-S-phenylsulfonimidoyl)-pent-2-ene | 172748-27-5

• 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: (+)-(Z,S)-4-methyl-1-(N-methyl-S-phenylsulfonimidoyl)-pent-2-ene
• 英文别名: (+)-(Z,S)-N-methyl-S-(4-methyl-2-pentenyl)-S-phenylsulfoximine；methylimino-[(Z)-4-methylpent-2-enyl]-oxo-phenyl-lambda6-sulfane；methylimino-[(Z)-4-methylpent-2-enyl]-oxo-phenyl-λ6-sulfane
• CAS: 172748-27-5
• 化学式: C₁₃H₁₉NOS
• 分子量: 237.366
• InChiKey: QMYPZDNWXQJJFA-PTZVLDCSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 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：

  (+)-(Z,S)-4-methyl-1-(N-methyl-S-phenylsulfonimidoyl)-pent-2-ene 在 咪唑 、 正丁基锂 、 1,2-diazabicyclo[5.4.0]undec-7-ene 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 8.25h， 生成 (-)-(Z,SS,2R,3R)-5-[N-methyl-S-phenylsulfonimidoyl]-3-isopropyl-2-triethylsilanoxypent-4-enoic acid ethyl ester
  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 125.0h， 生成 (+)-(Z,S)-4-methyl-1-(N-methyl-S-phenylsulfonimidoyl)-pent-2-ene
  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 disubstituted C-silylated homoallylic alcohols from lithiated allylic and vinylic sulfoximines
  作者：Hans-Joachim Gais、Harald Müller、Jürgen Decker、Rüdiger Hainz

  DOI：10.1016/0040-4039(95)01554-x

  日期：1995.10

  hydroxyalkylation of allylic N-methyl sulfoximines 1–4 gave with ≥ 95% de the anti-Z-configurated homoallylic alcohols 5–9. Lithiation of 6b and 8b with MeLi readily produced the lithiated vinylic sulfoximines (Z)-12 and (Z)-13, respectively. Ni-catalyzed substitution of (Z)-12 and (Z)-13 with PhLi and 1,5-silyl migration yielded with ≥ 98% de the disubstituted C-silylated homoallylic alcohols (Z)-14 and (Z)-15

  锂化，钛和烯丙基N-甲基亚磺酰亚胺的羟烷基化1-4与≥95％，得到解的防Z -构型高烯丙醇5-9。用MeLi将6b和8b锂化，分别容易地产生锂化的乙烯基亚砜亚砜（Z）-12和（Z）-13。镍催化的（取代Ž） - 12和（Ž） - 13用PhLi和1,5-甲硅烷迁移与≥98％，得到DE的二取代C-甲硅烷基化高烯丙醇（Ž） -分别为图14和（Z）-15。（ž） - 15由此从（获得Ž） - 13有一个EE的≥98百分数。
• N-Methylsulfonimidoyl-Substituted (2-Alkenyl)titanium Complexes: Application to the Synthesis of β- and δ-Sulfonimidoyl-Substituted Chiral Homoallylic Alcohols, X-ray Crystal Structure Analysis, and Fluxional Behavior
  作者：Hans-Joachim Gais、Rüdiger Hainz、Harald Müller、Peter Richard Bruns、Nicole Giesen、Gerhard Raabe、Jan Runsink、Sabine Nienstedt、Jürgen Decker、Marcel Schleusner、Jochen Hachtel、Ralf Loo、Chang-Wan Woo、Parthasarathi Das

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

  日期：2000.12

  corresponding (Z)-configured allylic sulfoximines, which were subsequently isomerized by DBU to preferentially yield the (E)-isomers. Titanation of lithiated (E)-configured allylic sulfoximines with ClTi(OiPr)3 furnished the corresponding bis(2-alkenyl)diisopropyloxytitanium(IV) complexes, which reacted with aldehydes in the presence of ClTi(OiPr)3 with high regio- and diastereoselectivities at the γ-position

  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
• Stereoselective hydroxyalkylation of titanated allyl sulfoximines at the α-as well as the γ-position through variation of the titanation reagent
  作者：Rüdiger Hainz、Hans-Joachim Gais、Gerhard Raabe

  DOI：10.1016/0957-4166(96)00318-7

  日期：1996.9

  Titanation of the lithioallyl sulfoximines E-2 and 2-2 with ClTi(NEt(2))(3) gives allyltitanium species which react with aldehydes highly regio- and diastereoselectively at the alpha-position to form the syn-alpha-hydroxalkyl allyl sulfoximines E-3 and Z-3, respectively. With ClTi(OiPr)(3) as the titanation reagent anti-gamma-hydroxyalkyl vinyl sulfoximines are obtained instead with equally high selectivities. NMR spectroscopic evidence points to the formation of the monoallyltitanium sulfoximine E-l upon reaction of E-2 withClTi(NEt(2))(3). Copyright (C) 1996 Elsevier Science Ltd
• 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
  作者：Shashi Kant Tiwari、Hans-Joachim Gais、Andreas Lindenmaier、Gadamsetti Surendra Babu、Gerhard Raabe、Leleti Rajender Reddy、Franz Köhler、Markus Günter、Stefan Koep、Vijaya Bhaskara Reddy Iska

  DOI：10.1021/ja061152i

  日期：2006.6.1

  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.