(+)-(S)-S-(1-cyclopenten-1-ylmethyl)-N-(p-tolylsulfonyl)-S-phenylsulfoximine | 167389-36-8

• 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: (+)-(S)-S-(1-cyclopenten-1-ylmethyl)-N-(p-tolylsulfonyl)-S-phenylsulfoximine
• CAS: 167389-36-8
• 化学式: C₁₉H₂₁NO₃S₂
• 分子量: 375.513
• InChiKey: DGRZMAKAEPZHSN-DEOSSOPVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.32
• 重原子数：
  25.0
• 可旋转键数：
  5.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  63.57
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (+)-(S)-S-(1-cyclopenten-1-ylmethyl)-N-(p-tolylsulfonyl)-S-phenylsulfoximine 在 四(三苯基膦)钯 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 1.84h， 生成 N-((S)-1-Cyclopent-1-enyl-ethyl)-4-methyl-benzenesulfonamide
  参考文献：
  名称：

  Palladium-Catalyzed Rearrangement of Allylic Sulfoximines:  Application to the Asymmetric Synthesis of Chiral Allylic Amines

  摘要：

  The palladium(0)-catalyzed reactions of the primary and secondary allylic sulfoximines 7, 9, 11, 13, 15, 17, and 19 gives allylic sulfinamides without 1,3-allylic rearrangement. These compounds were not isolated but were converted to their corresponding N-tosyl allylic amines, primary and secondary 8, 10, 12, 14, 16, 18, and 20, respectively. In the case of the optically active secondary allylic sulfoximines 17 and 19, chiral N-tosyl allylic secondary amines were formed in high enantiomeric purities.

  DOI：

  10.1021/jo9605105
• 作为产物：
  描述：

  (+)-(S_S)-S-methyl-S-phenyl-N-(p-tolylsulphonyl)sulphoximine 在 正丁基锂 、 甲基磺酰氯 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 作用下， 反应 3.67h， 生成 (+)-(S)-S-(1-cyclopenten-1-ylmethyl)-N-(p-tolylsulfonyl)-S-phenylsulfoximine
  参考文献：
  名称：

  Palladium-Catalyzed Rearrangement of Allylic Sulfoximines:  Application to the Asymmetric Synthesis of Chiral Allylic Amines

  摘要：

  The palladium(0)-catalyzed reactions of the primary and secondary allylic sulfoximines 7, 9, 11, 13, 15, 17, and 19 gives allylic sulfinamides without 1,3-allylic rearrangement. These compounds were not isolated but were converted to their corresponding N-tosyl allylic amines, primary and secondary 8, 10, 12, 14, 16, 18, and 20, respectively. In the case of the optically active secondary allylic sulfoximines 17 and 19, chiral N-tosyl allylic secondary amines were formed in high enantiomeric purities.

  DOI：

  10.1021/jo9605105

文献信息

• Diastereoselective Reactions and Rearrangements of Chiral Allylic Sulfoximines
  作者：Stephen G. Pyne、Z. Dong、D. M. David、G. W. O'Meara

  DOI：10.1080/10426509708545524

  日期：1997.1.1

  nucleophilic and electrophilic chemistry of chiral allylic sulfominines and their alkyl sulfoximine counterparts are described including the synthesis of highly functionalised cyclopropanes derivatives. The synthesis of primary and secondary N-tosyl allylic amines via the palladium(0) catalysed rearrangement of allylic sulfoximines to allylic sulfinamides is also described.

  摘要：描述了手性烯丙基亚磺胺及其烷基亚砜亚胺对应物的亲核和亲电化学，包括高度官能化的环丙烷衍生物的合成。还描述了通过钯 (0) 催化的烯丙基亚砜亚胺重排为烯丙基亚磺酰胺的伯和仲 N-甲苯磺酰基烯丙基胺的合成。
• 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.