Conjugate addition reactions with lithium diallylcuprate

House, Herbert O.; Fischer, W. F.

doi:10.1021/jo01263a087

Cited by 82 publications

(32 citation statements)

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“…Conceptually direct approach for their synthesis involves a Michael-type reaction between an acetylenic unit and a conjugated enone. The most common cuprate chemistry and dilithium trialkynylcuprate complexes fail to effect the conjugate addition of an alkynyl group to a conjugated enone [3,4]. Numerous attempts have been made to bridge this gap in synthetic methodology [5][6][7][8][9][10][11][12][13][14].…”

Section: Introductionmentioning

confidence: 99%

1, 4-Addition of Terminal Alkynes to Conjugated Enones in Water Using Green Catalyst Bis[(l)prolinato-N,O]Zn—An Environmentally Benign Protocol

2010

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Section: Introductionmentioning

confidence: 99%

1, 4-Addition of Terminal Alkynes to Conjugated Enones in Water Using Green Catalyst Bis[(l)prolinato-N,O]Zn—An Environmentally Benign Protocol

2010

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“…Moreover, the method most commonly used for regioselective addition of alkyl and alkenyl groups, namely the use of copper(I) reagents 26,27 has been thwarted by the inertness of copper(I)-alkynylides. 28 This has lead to the use of alkynes as dummy ligands in mixed organocuprates to ensure the selective transfer of more reactive groups (Eq. 1).…”

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confidence: 99%

Stereoselective Conjugate Addition Reactions Using In Situ Metallated Terminal Alkynes and the Development of Novel Chiral P,N-Ligands

Fujimori¹,

Knöpfel²,

Zarotti³

et al. 2007

Bulletin of the Chemical Society of Japan

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In this account, new methods for the catalytic and stereoselective conjugate addition of terminal alkynes are described. Our laboratories have disclosed asymmetric addition reactions to aldehydes and imines using a combination of a zinc or copper salt and a terminal alkyne. Under these conditions, terminal alkyne is transformed in situ into an alkynyl metal species. Recently, it was found that these in situ generated alkynyl metal species can undergo conjugate additions to alkylidene malonate-type acceptors. In the zinc(II) triflate-catalyzed system, a highly diastereoselective conjugate addition has been realized using a chiral oxazepene acceptor. Subsequently, alternative conjugate addition protocols have been developed which employ a terminal alkyne, substoichiometric amounts of copper and a highly eletrophilic Meldrum's acid derived acceptor. This reaction can be made enantioselective using a novel atropisomeric P,Nligand (PINAP). With this ligand, excellent enantioselectivities can be achieved for the conjugate addition of aromatic alkynes to various Meldrum's acid derived acceptors.

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“…Good yields can only be obtained with doubly activated esters as shown in (14) and (15). 176,177 The importance of the conjugate addition has prompted numerous searches for procedures and methods to effect asymmetric induction. [178][179][180][181][182] One recent example is the use of (S)-2-(methoxymethyl)pyrrolidine as a chiral copper ligand (Scheme 48).…”

Section: Copper Enolates and Enolates From Cupratesmentioning

confidence: 99%