(+)-(S)-S-(1-cyclopen-1-ylmethyl)-N-methyl-S-phenylsulfoximine | 131865-69-5

• 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: (+)-(S)-S-(1-cyclopen-1-ylmethyl)-N-methyl-S-phenylsulfoximine
• 英文别名: (S)-N-methyl-S-(1-cyclopenten-1-ylmethyl)-S-phenylsulfoximine
• CAS: 131865-69-5
• 化学式: C₁₃H₁₇NOS
• 分子量: 235.35
• InChiKey: VFMHBZFQVFQNLA-INIZCTEOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.25
• 重原子数：
  16.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  29.43
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (+)-(S)-S-(1-cyclopen-1-ylmethyl)-N-methyl-S-phenylsulfoximine 在 三异丙氧基氯化钛 、 盐酸 、 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 、 溶剂黄146 为溶剂， 反应 48.25h， 生成 (S)-methylphenylsulfoxide
  参考文献：
  名称：

  不对称合成带有支链羟烷基侧链的受保护 β-取代和 β,β-二取代 β-氨基酸，以及烯丙基亚砜亚胺和醛具有三个连续立体中心的受保护 1,3-氨基醇的不对称合成

  摘要：

  我们描述了一种不对称合成的新方法，从烯丙基亚砜亚胺和醛，N,O-保护的、环状和非环状的、β-取代的和 β,β-二取代的 δ-羟基-β-氨基酸和 N,O-受保护的 1,3-氨基醇，均具有三个连续的立体中心。在连续锂化和钛化后用醛处理对映体纯的无环烯丙基亚砜亚胺，得到具有高区域选择性和非对映选择性的磺酰亚胺酰基取代的高烯丙醇。非对映体纯的、环状的、磺酰亚胺酰基取代的高烯丙醇以类似的方式从相应的对映体纯的环状烯丙基亚砜亚胺和异丁醛合成。磺酰亚胺酰基取代的高烯丙醇的高度非对映选择性胺化产生仲和叔碳原子并形成磺酰亚胺酰基取代的、受保护的 1,3-氨基醇（恶嗪酮）是通过氨基甲酸酯方法实现的，通过相应的环化与 nBuLi 锂化后的氨基甲酸酯。磺酰亚胺酰基取代的单环和双环恶嗪酮通过两种不同的途径转化为受保护的、无环和环状的、β-取代和 β,β-二取代的 β-氨基酸和受保护的 1,3-氨基醇：碳负离子途径和取代路线。碳负离子途径包括：(1)

  DOI：

  10.1002/ejoc.200390210
• 作为产物：
  描述：

  (S)-((Z)-((R)-2-((S)-2-methyl-1-((triethylsilyl)oxy)propyl)cyclopentylidene)methyl)(methylimino)(phenyl)-l6-sulfanone 在 盐酸 、 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 、 溶剂黄146 为溶剂， 反应 23.0h， 生成 (+)-(S)-S-(1-cyclopen-1-ylmethyl)-N-methyl-S-phenylsulfoximine
  参考文献：
  名称：

  不对称合成带有支链羟烷基侧链的受保护 β-取代和 β,β-二取代 β-氨基酸，以及烯丙基亚砜亚胺和醛具有三个连续立体中心的受保护 1,3-氨基醇的不对称合成

  摘要：

  我们描述了一种不对称合成的新方法，从烯丙基亚砜亚胺和醛，N,O-保护的、环状和非环状的、β-取代的和 β,β-二取代的 δ-羟基-β-氨基酸和 N,O-受保护的 1,3-氨基醇，均具有三个连续的立体中心。在连续锂化和钛化后用醛处理对映体纯的无环烯丙基亚砜亚胺，得到具有高区域选择性和非对映选择性的磺酰亚胺酰基取代的高烯丙醇。非对映体纯的、环状的、磺酰亚胺酰基取代的高烯丙醇以类似的方式从相应的对映体纯的环状烯丙基亚砜亚胺和异丁醛合成。磺酰亚胺酰基取代的高烯丙醇的高度非对映选择性胺化产生仲和叔碳原子并形成磺酰亚胺酰基取代的、受保护的 1,3-氨基醇（恶嗪酮）是通过氨基甲酸酯方法实现的，通过相应的环化与 nBuLi 锂化后的氨基甲酸酯。磺酰亚胺酰基取代的单环和双环恶嗪酮通过两种不同的途径转化为受保护的、无环和环状的、β-取代和 β,β-二取代的 β-氨基酸和受保护的 1,3-氨基醇：碳负离子途径和取代路线。碳负离子途径包括：(1)

  DOI：

  10.1002/ejoc.200390210

文献信息

• Asymmetric Synthesis of Densely Functionalized Medium-Ring Carbocycles and Lactones through Modular Assembly and Ring-Closing Metathesis of Sulfoximine-Substituted Trienes and Dienynes
  作者：Michal Lejkowski、Prabal Banerjee、Sabine Schüller、Alexander Münch、Jan Runsink、Cornelia Vermeeren、Hans-Joachim Gais

  DOI：10.1002/chem.201103060

  日期：2012.3.19

  (S)‐diastereomer delivered in a cascade of cross metathesis and RCDEM 22‐membered macrocycles. RCDEM of cyclic trienes furnished bicyclic carbocycles with a bicyclo[7.4.0]tridecane and bicyclo[9.4.0]pentadecane skeleton. Selective transformations of the sulfoximine‐ and bissilyloxy‐substituted carbocycles were performed including deprotection, cross‐coupling reaction and reduction of the sulfoximine moiety

  已经开发出稠密官能化的7-11元碳环和9-11元内酯的不对称合成。它的关键步骤是用模块组装硫磺亚胺取代的C和O系三烯和C系二烯，以及它们在Ru催化下的闭环二烯和烯炔复分解（RCDEM和RCEYM）。C链状三烯和二烯的合成包括以下步骤：1）对映体纯的钛酸烯丙基亚砜基亚砜与不饱和醛的羟烷基化，2）烯基亚砜基亚砜的α-锂化，3）α的烷基化，羟基烷基化，甲酰化和酰化-硫代链烯基亚砜亚胺，以及4）将格氏试剂添加到α-甲酰基（酰基）烯基亚砜基亚砜。亚砜亚胺基团在步骤1）和4）中提供了高不对称诱导作用。用第二代Ru催化剂对亚砜亚胺取代的三烯进行的RCDEM立体选择性地提供了相应的功能化7-11元碳环。非对映异构的甲硅烷氧基取代的1,6,12-三烯的RCDEM显示出反应性上的有趣差异。而（R）-非对映异构体给出了11元的碳环，（S）非对映异构体以交叉复分解和RCDEM 22元大环化合物的级联传递。环状三烯的RCDEM为双环碳环提供了双环[7
• Asymmetric Synthesis of Unsaturated, Fused Bicyclic Proline Analogues through Amino Alkylation of Cyclic Bis(allylsulfoximine)titanium Complexes and Migratory Cyclization of δ-Amino Alkenyl Aminosulfoxonium Salts
  作者：Stefan Koep、Hans-Joachim Gais、Gerhard Raabe

  DOI：10.1021/ja030324y

  日期：2003.10.1

  syn)-configured, delta-sulfoximine substituted, cyclic gamma,delta-unsaturated alpha-amino acid esters with high regio- and diastereoselectivities in good yields. Activation of the N-methyl sulfoximine group of these amino acid derivatives through methylation with Me(3)OBF(4) afforded in nearly quantitative yields the corresponding (dimethylamino)sulfoxonium salts. A novel migratory cyclization of these

  描述了由环状双（烯丙基亚砜亚胺）钛配合物和 N-叔丁基磺酰基亚氨基乙酯不对称合成新的 Delta(3a,4)-不饱和稠合双环脯氨酸类似物。用亚氨基酯处理对映体纯的五元、六元、七元和八元环状双（烯丙基亚砜亚胺）钛络合物，得到相应的 (E,syn)-和 (Z,syn)-构型的混合物，δ -亚砜亚胺取代的环状γ，δ-不饱和α-氨基酸酯，具有高产率和非对映选择性。这些氨基酸衍生物的 N-甲基亚砜亚胺基团通过甲基化与 Me(3)OBF(4) 活化，以几乎定量的方式提供相应的 (二甲氨基) 锍盐。这些盐与 DBU 的新型迁移环化通过异构化为相应的烯丙基（二甲氨基）锍盐和（二甲氨基）锍基团的分子内取代得到对映和非对映异构纯、双环、N-叔丁基磺酰基保护的脯氨酸类似物具有六元和八元不饱和碳环。烯基（二甲氨基）锍盐的环化与双键的构型无关。作为进一步的反应产物，以良好的收率获得≥99％ee的N，N-二甲基苯基亚
• Regio- and Enantioselective Substitution of Primary Endocyclic Allylic Sulfoximines with Organocopper and Organocuprate Reagents. The Importance of Iodide for the Allylic Substitution with Organocopper Compounds
  作者：Hans-Joachim Gais、Harald Mueller、Joerg Bund、Matthias Scommoda、Jochen Brandt、Gerhard Raabe

  DOI：10.1021/ja00114a009

  日期：1995.3

  The endocyclic N-substituted allylic sulfoximines 17-20 and 26 were synthesized from the corresponding cycloalkanones and the various (S)-S-(lithiomethyl)-S-phenylsulfoximine in enantiomerically pure form in yields of 60-70% in a process involving the isomerization of the intermediate vinylic sulfoximines. Desilylation of 26 gave the parent N-H sulfoximine 27 from which the N-sulfonylsulfoximines 28 and 29 were prepared. The X-ray crystal structure of 28 was determined. The allylic sulfoximines 17-20 and 26-29 did not racemize or rearrange thermally to the corresponding allylic sulfinamides. Reaction of the allylic sulfoximines 18, 28, and 29 with the organocuprate reagents 2/LiI, 35/LiI, and 47/LiI led with alpha-selectivities of 92:8 to 99:1 to the endocyclic alkenes 39 in good to high yields. Reaction of 17-20, 28, and 29 with the organocopper reagents 5/LiI, 30/LiI, 31/LiI, 32/LiI, 33/LiI, 34/LiI, and 37/LiI in the presence of BF3 resulted in the formation of the exocyclic alkenes 38, 41, 43, and 45, respectively, in good to high yields with gamma-selectivities of 80:20 to 99:1. The sulfonimidoyl group imparts asymmetric induction to the substitution in the range of 27-90% ee. The (S)-sulfonimidoyl group leads to a preferential bond formation from the si side of the double bond. From the sulfoximines 18 and 26-29 the N-methylsulfoximine 18 and the N-tosylsulfoximine 28 showed the highest and lowest reactivity with the butylcopper reagent 32/LiI in the presence of BF3 respectively, while in the absence of BF3 only 29 reacted. The Lewis acid most likely serves to activate the N-methyl- and N-tosylsulfoximines or intermediates thereof through coordination at the sulfonimidoyl and sulfonyl group. Reaction of the sulfoximines 18 and 29 with pure Me(3)SiCH(2)Cu (34) revealed a strong rate acceleration by LiI and an even stronger one by Bu(4)NI. This points to the existence of a heteroleptic cuprate or a related compound as reactive species. In substitutions with the Yamamoto reagents RCu/MX/BF3, the halide is important and a reaction between RCu and BF3 does not have, at least in the case of allylic sulfoximines, to be invoked. In reactions of 17-20 besides the alkenes, the sulfinamide ent-4 was formed with an ee value of 97% in high yield with retention of configuration. The absolute configuration of the exocyclic alkenes 38, 41, and 45 was determined by ozonolysis to the corresponding cycloalkanones followed by their conversion to the corresponding lactones and/or CD measurement of the former.
• 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.
• Regioselective and enantioselective substitution of allylic sulfoximines with organocopper reagents. A versatile approach to optically active isocarbacyclins
  作者：Joerg Bund、Hans Joachim Gais、Irene Erdelmeier

  DOI：10.1021/ja00004a071

  日期：1991.2