(+)-(R)-1-<4-(1-ethoxyethoxy)butyl>2-methylenecyclopentane | 131865-70-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+)-(R)-1-<4-(1-ethoxyethoxy)butyl>2-methylenecyclopentane
• 英文别名: (1R)-1-[4-(1-ethoxyethoxy)butyl]-2-methylidenecyclopentane
• CAS: 131865-70-8
• 化学式: C₁₄H₂₆O₂
• 分子量: 226.359
• InChiKey: FMGUMVNTOQUHSU-KZUDCZAMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  16
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (-)-(S)-S-(cyclopentylidenemethyl)-N-methyl-S-phenylsulfoximine 在 二甲基硫 、 三氟化硼乙醚 、 lithium methanolate 作用下， 以 四氢呋喃 、 乙醚 、 甲苯 为溶剂， 反应 4.0h， 生成 (+)-(R)-1-<4-(1-ethoxyethoxy)butyl>2-methylenecyclopentane
  参考文献：
  名称：

  Regioselective and enantioselective substitution of allylic sulfoximines with organocopper reagents. A versatile approach to optically active isocarbacyclins

  摘要：

  DOI：

  10.1021/ja00004a071

文献信息

• 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.
• 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