(S)-N-methyl-S-(1-cyclohexen-1-ylmethyl)-S-phenylsulfoximine | 167389-29-9

• 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)-N-methyl-S-(1-cyclohexen-1-ylmethyl)-S-phenylsulfoximine
• 英文别名: Cyclohexen-1-ylmethyl-methylimino-oxo-phenyl-lambda6-sulfane；cyclohexen-1-ylmethyl-methylimino-oxo-phenyl-λ6-sulfane
• CAS: 167389-29-9
• 化学式: C₁₄H₁₉NOS
• 分子量: 249.377
• InChiKey: GEBIFRBPXMROJH-KRWDZBQOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 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：

  (S)-N-methyl-S-(1-cyclohexen-1-ylmethyl)-S-phenylsulfoximine 在 盐酸 、 m-C₆H₄CO₃H 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 8.0h， 以96%的产率得到(cyclohex-1-enyl)methyl phenyl sulfone
  参考文献：
  名称：

  A Method for the Conversion of Sulfoximines to Sulfones: Application to Polymer-Bound Sulfoximines and to the Synthesis of Chiral Sulfones

  摘要：

  Reaction of N-alkyl, N-aryl, and N-H sulfoximines with m-chloroperbenzoic acid cleanly gives the corresponding sulfones in high yield. In the case of the cleavage of N-alkyl and N-arylsulfoximines, formation of the corresponding nitroso compounds as the other reaction product was proven. Starting from enantio- and diastereopure sulfoximines, a number of chiral sulfones, including the axially chiral sulfone 6 and the sulfonyl-functionalized homoallylic alcohol 8, have been prepared. Reaction of the enantiopure sulfoximine 30 with Merrifield resin gave the polymer-bound sulfoximine 32. Oxidative cleavage of 32 afforded the sulfone 16 in high yield. Deprotonation of the sulfoximine resin 32 and reaction of Li-32 with benzaldehyde and propanal furnished the beta-hydroxysulfoximine resins 33a and 33b, respectively. Oxidative cleavage of 33a and 33b readily afforded the beta-hydroxy sulfones 14a and 14b, respectively.

  DOI：

  10.1002/(sici)1099-0690(200004)2000:8<1457::aid-ejoc1457>3.0.co;2-g
• 作为产物：
  描述：

  N,S-dimethyl-S-phenylsulfoximine 在 sodium methylate 作用下， 以 四氢呋喃 为溶剂， 反应 96.0h， 生成 (S)-N-methyl-S-(1-cyclohexen-1-ylmethyl)-S-phenylsulfoximine
  参考文献：
  名称：

  由烯丙基铝亚砜肟亚胺和α-杂醛不对称合成取代的均烯丙基醇，卤代甲基四氢呋喃和氯氨基砜。

  摘要：

  描述了分别由烯丙基硫代肟基15和α-杂醛2和23不对称合成碘甲基取代的双环四氢呋喃22和氯氨基砜30。给出了不对称合成氯甲基四氢呋喃和氯氨基砜的其他例子。30个特征的合成是关键步骤，其羟基的立体选择性Cl-取代在相邻基团的作用下被氨基磺氧鎓基团转化为磺酰基。[反应：请参见文字]。

  DOI：

  10.1021/ol0627606

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 2,3-Dihydrofurans and of Unsaturated Bicyclic Tetrahydrofurans through α-Elimination and Migratory Cyclization of Silyloxy Alkenyl Aminosulfoxonium Salts. Generation and Intramolecular O,Si-Bond Insertion of Chiral Disubstituted β-Silyloxy Alkylidene Carbenes
  作者：Hans-Joachim Gais、Leleti R. Reddy、Gadamsetti S. Babu、Gerhard Raabe

  DOI：10.1021/ja030501v

  日期：2004.4.1

  but suffered a novel migratory cyclization with formation of the enantio- and diastereomerically pure bicyclic tetrahydrofurans 9a, 9b, and ent-9c, respectively. It is proposed that the 1-alkenyl sulfoxonium salts 8a, 8b, and ent-8c are isomerized to the allylic aminosulfoxonium salts 10a, 10b, and ent-10c, respectively, which then suffer an intramolecular substitution of the (dimethylamino)sulfoxonium

  用醛处理衍生自 β-甲基取代的无环烯丙基亚砜亚胺 13a 和 13b 的双（烯丙基亚砜亚胺）钛络合物，以高选择性得到相应的亚砜亚胺取代的高烯丙醇，其被分离为甲硅烷基醚 15a-h。亚砜亚胺 15a-h 的甲基化得到氨基亚砜盐 5a-h，在用 LiN(H)tBu 处理后，以高产率得到对映体和非对映体纯甲硅烷基取代的 2,3-二氢呋喃 4a-h。用 p-MeOC(6)H(4)CHO 处理衍生自环状烯丙基亚砜亚胺 17a、17b 和 ent-17c 的钛配合物，以高选择性提供相应的亚砜亚胺取代环状高烯丙醇，分离为甲硅烷基醚分别参见 18a、18b 和 ent-18c。亚砜亚胺 18a、18b、和 ent-18c 分别提供氨基锍盐 8a、8b 和 ent-8c，其用 LiN(H)t-Bu 处理得到对映和非对映异构纯稠合双环 2,3-二氢呋喃 6a、6b 和 ent- 6c，分别以良好的产量。提出 1-烯基氨基锍盐
• 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
• 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.