Transmetalation Reactions Producing Organocopper Reagents

Knöchel, Paul; Betzemeier, Bodo

doi:10.1002/3527600086.ch2

Cited by 20 publications

(11 citation statements)

References 127 publications

(178 reference statements)

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“…A reação entre sais de cobre(I) e organometálicos pode levar à formação de cupratos de diversas estequiometrias. 42 No caso do CuCN, apenas duas estequiometrias de organometálico/sal são geralmente utilizadas, 1:1 e 2:1, que geram respectivamente RCuCNLi e R 2 CuCNLi 2 . Se apenas os cianocupratos de Lipshutz pudessem ser formados, e não cupratos de maiores estequiometrias, as reações 4 e 11 deveriam ter levado, a princípio, ao mesmo resultado.…”

Section: 35a 335bunclassified

Novos aspectos e aplicações da química de teluranas e de teluretos orgânicos

Cunha¹

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Aproveito este espaço para agradecer a todos que contribuiram em minha formação até o presente. Ao Prof. J. V. Comasseto, pela orientação e sobretudo pela generosidade em conceder autonomia para a realização das atividades no laboratório, interferindo nos momentos apropriados para acertar o leme que norteou minhas atividades. E, além disso, pelos bons momentos de descontração e de troca de idéias nas reuniões de grupo fora do laboratório. Ao Prof. Paulo Sumodjo, pela orientação complementar em instâncias científicas, éticas e culturais e pela amizade. Ao Prof. Julio Schpector, pelas colaborações, discussões e amaizade que fundamentarma boa parte deste trabalho. Ao Prof. Nicola Petragnani, pelos agradáveis momentos de conversas e discussões, dedico minha admiração e respeito. A Profa. Helena Ferraz, pelo ótimo convívio nestes anos de graduação e pós-graduação. Aos demais professores que sempre me receberam para discussões e troca de idéias: Prof. José

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Section: 35a 335bunclassified

Novos aspectos e aplicações da química de teluranas e de teluretos orgânicos

Cunha¹

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“…Therefore, a stochiometric ACCR of (Z)-2 and (E)-2 with organocuprates could give access to highly substituted homoallyl alcohols of type (E)-9 and (Z)-9, which are not readily available otherwise. [15,16] This route to (E)-9 and (Z)-9 should benefit from 1) the facile synthesis of copper reagents including those carrying functional groups; [17] 2) the high reactivity of alkenyl cuprates of type (Z)-8 and (E)-8; and 3) the ready availability of the alkenyl sulfoximines (Z)-1 and (E)-1 [18][19][20][21] as well as their a-lithio derivatives (Z)-2 and (E)-2, respectively. [1,2,19,[22][23][24] Support for the feasibility of a synthesis of sulfoximinesubstituted HO alkenyl cuprates of type (E)-7 and (Z)-7 and their 1,2-MR came from studies of the carbamoyloxysubstituted HO alkenyl cuprates (E)-11 (Scheme 4).…”

Section: Introductionmentioning

confidence: 99%

Anionic Cross‐Coupling Reaction of α‐Metallated Alkenyl Sulfoximines and Alkenyl Sulfoximines with Cuprates Featuring a 1,2‐Metal‐Ate Rearrangement of Sulfoximine‐Substituted Higher Order Alkenyl Cuprates and an α‐Metallation of Alkenyl Sulfoximines by Cuprates

Gais

Rao

Loo

2008

Chemistry A European J

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(E)- and (Z)-configured alpha-lithioalkenyl sulfoximines, which are available through lithiation of the corresponding alkenyl sulfoximines, undergo a anionic cross-coupling reaction (ACCR) with organocuprates with formation of the corresponding alkenyl cuprates and sulfinamide. The alkenyl cuprates can be trapped by electrophiles. The ACCR presumably proceeds via the formation of a higher-order sulfoximine-substituted alkenyl cuprate, which undergoes a 1,2-metal-ate rearrangement whereby the sulfoximine group acts as the nucleofuge. The parent (E)- and (Z)-configured alkenyl sulfoximines suffer upon treatment with an organocuprate a deprotonation at the alpha-position with formation of the corresponding alpha-cuprioalkenyl sulfoximines. These derivatives also enter into a similar ACCR with organocuprates. The ACCR of sulfoximines substituted homoallylic alcohols allows a stereoselective access to enantio- and diastereopure substituted homoallylic alcohols.

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“…Finally, we used milder organometallic reagents compatible with a wide range of functional groups. The reactions of 2 with mixed copper−zinc reagents (RZn(Cu)X or RCu(CN)ZnX·2LiCl) and diorganozinc reagents (R 2 Zn) did not provide amide 8 (even with catalytic Pd(PPh 3 ) 4 ), whereas contrasting results were obtained with monoorganozinc reagents (R 3 ZnX)…”

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confidence: 98%

“…This reliable methodology provides a viable alternative to carbon monoxide and a new use for phosgene, or its substitutes, as a carbonylating reagent to synthesize tertiary amides, mostly when corresponding acids are not easily available. Due to the peculiar reactivity of organocopper reagents, work is now in progress to extend the scope of the reaction to functionalized substrates or reagents.…”

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confidence: 99%