trimethylsilylmethylcopper | 48003-18-5

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: trimethylsilylmethylcopper
• CAS: 48003-18-5
• 化学式: C₄H₁₁CuSi
• 分子量: 150.763
• InChiKey: MICQEAJTHHUEAJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  6
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  bis(η5-trimethylsilylcyclopentadienyl)bis(trimethylsilylethynyl)-titanium 、 trimethylsilylmethylcopper 以 乙醚 为溶剂， 以90%的产率得到
  参考文献：
  名称：

  铜（I）和银（I）与 η1-键合的烷基、乙烯基和芳基配体的单体双（η2-炔）配合物

  摘要：

  化合物[(η5-C5H4SiMe3)2Ti(C⋮CSiMe3)2]MR（简写为[1·MR]；M=Cu：R=Me（5）、CH2SiMe3（6）、Et（7））的两条合成路线， nBu (8), C(H)CH2 (9), C6H2Me3-2,4,6 (13), C6H4Me-4 (14), C6H4OMe-4 (15), C6H4NMe2-4 (16), C6H5 (17) ; M = Ag: R = C6H2Me3-2,4,6 (18)) 进行了描述。这些化合物包含单体 MR 实体，它们通过有机金属 3-钛-1,4-戊二炔 [(η5-C5H4SiMe3)2Ti(C⋮CSiMe3)2] (1) 的两个炔烃配体 η2 键合。5、13 和 18 的 X 射线结构已经解决。5 晶体为单斜晶系，空间群 C2/c，a = 19.477(1) A, b = 10.3622(6) A, c = 16.395(1)

  DOI：

  10.1021/ja954041k
• 作为产物：
  描述：

  copper(l) iodide 、 trimethylsilylmethyllithium 以 乙醚 为溶剂， 以55%的产率得到trimethylsilylmethylcopper
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1021/ja00114a009

文献信息

• Elongated Gilman Cuprates: The Key to Different Reactivities of Cyano- and Iodocuprates
  作者：Maria Neumeier、Ruth M. Gschwind

  DOI：10.1021/ja501055c

  日期：2014.4.16

  cuprates. In addition, the effect of these copper-rich complexes on the yields of cross-coupling reactions with an alkyl halide was tested, resulting in reduced yields for iodocuprates. Thus, this study gives an explanation for the thus far confusing results of both similar and different reactivities of cyano- and iodocuprates. In the case of small substituents the produced alkyl copper precipitates and

  过去，关于氰基与碘铜酸盐的特殊反应性的长期且非常有争议的讨论集中在高阶铜酸盐结构的存在上。后来的大量结构研究证明了碘和氰基吉尔曼铜酸盐及其后续中间体的结构等效性。对于二甲基铜酸盐，也显示出类似的反应性。然而，关于氰铜酸盐具有更高反应性的报道在许多合成工作组中顽固地存在。在这项研究中，我们提出了氰基和碘铜酸盐之间的另一种结构差异，这与双方的结果一致。关键是在反应过程中烷基铜可能掺入碘中，但不会掺入氰基吉尔曼铜酸盐中。在具有高溶解性取代基（R = Me3SiCH2）的铜酸盐的例子中，我们表明在反应过程中碘铜酸盐的情况下形成了几种富含铜的配合物，它们消耗额外的碘铜酸盐并提供较低的反应性。为了证实这一点，合成了各种高溶解性的富铜配合物，并通过核磁共振光谱方法研究了它们的分子式、平衡位置、单体及其聚集趋势，揭示了扩展的碘吉尔曼铜酸盐。此外，还测试了这些富含铜的配合物对与卤代烷交叉偶联反应产率的影响，
• Rossi, Renzo; Carpita, Adriano; Bellina, Fabio, Gazzetta Chimica Italiana, 1990, vol. 120, p. 457 - 464
  作者：Rossi, Renzo、Carpita, Adriano、Bellina, Fabio、De Santis, Massimo、Veracini, Carlo Alberto

  DOI：——

  日期：——
• KLEIJN, H.;VERMEER, P., J. ORGANOMET. CHEM., 1986, 302, N 1, 1-4
  作者：KLEIJN, H.、VERMEER, P.

  DOI：——

  日期：——
• KLEIJN, H.;VERMEER, P., J. ORG. CHEM., 1985, 50, N 25, 5143-5148
  作者：KLEIJN, H.、VERMEER, P.

  DOI：——

  日期：——
• 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.