1,4-Addition of grignard reagents and 1,6-addition of lithium organocuprates to n,n-diethylsorbamide

Barbot, F.; Kadib-Elban, A.; Miginiac, Ph.

doi:10.1016/s0040-4039(00)94048-6

Cited by 30 publications

(8 citation statements)

References 7 publications

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“…To evaluate the reactivity of the amide towards nucleophilic addition, we carried out the initial reaction in the absence of ac atalyst at 0 8 8Ca nd at cryogenic temperatures (entries 1a nd 2). At 0 8 8Ct he 1,4-addition product was obtained with only 38 %y ield, similar to the result obtained by Miginiac et al, [8] whereas at À78 8 8Cn os ubstrate conversion was observed. Copper-based catalysts are known to promote the addition of various organometallics,i ncluding organomagnesium reagents,t oe xtended conjugated enones and enoates with very good selectivities.…”

Section: Catalytic Regio-and Enantioselectivealkylation Of Conjugated Dienyl Amidessupporting

confidence: 89%

Catalytic Regio‐ and Enantioselective Alkylation of Conjugated Dienyl Amides

2018

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A method for catalytic asymmetric alkylation of conjugated dienyl amides has been developed and it allows efficient and high‐yielding transformations of a wide range of polyconjugated amides into the corresponding chiral products. Smooth addition of organomagnesium reagents to relatively unreactive dienyl amides with excellent 1,6‐ and 1,4‐selectivities, as well as enantioselectivites above 90 %, is achieved owing to the complementary action of the Lewis acid and a chiral copper‐based catalyst.

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Section: Catalytic Regio-and Enantioselectivealkylation Of Conjugated Dienyl Amidessupporting

confidence: 89%

Catalytic Regio‐ and Enantioselective Alkylation of Conjugated Dienyl Amides

2018

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“…Thus for example, whereas the addition of Grignard reagents to sec-butylsorbate (1) had been reported to give a mixture of 1,2-, 1,4-and 1,6-adducts, Miginiac et al considered the additions to the corresponding diethylamide 2, a substrate particularly reluctant to 1,2-additions, of a variety of Grignard reagents in an extension of preliminary observations by Normant et al with the same compound (Scheme 2). 1 Moderate yields of the 1,4-adducts 3 were observed when 2 was treated with several alkylmagnesium bromides (33-55%), but MeMgI, TMS-CH 2 MgCl or alkynyl Grignard reagents did not react, and phenylmagnesium bromide as well as allylmagnesium bromide afforded intractable mixtures of products. However, other allylic Grignard reagents reacted with allylic rearrangement in good yields (60-80%) to afford the 1,4-adducts.…”

Section: Uncatalyzed Addition Of Organomagnesium and Organolithium Re...mentioning

confidence: 97%

Conjugate addition reactions of carbon nucleophiles to electron-deficient dienes

2010

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The conjugate addition reaction of carbon nucleophiles to electron-deficient olefins is one of the most reliable methods for selective C-C bond formation. However, the conjugate addition to the vinylogous electron-deficient dienes has been much less developed, as there is considerably more difficulty in controlling the regioselectivity of the addition to these extended conjugate systems due to the presence of three electrophilic sites, as well as the stereoselectivity. Although still underdeveloped, new approaches to tackle these challenges are beginning to emerge. Both transition-metal-catalyzed and organocatalytic approaches are currently being developed to cope with the main selectivity issues of this type of process: regioselectivity (1,2-, 1,4-, and 1,6-addition) and stereoselectivity (asymmetric formation of the new C-C bonds). In this tutorial review, we have surveyed representative examples to get an overview of the recent advances obtained in the scope of the conjugate addition reaction of carbon nucleophiles to electron-deficient dienes.

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“…Inspired by these seminal studies, the addition of cuprates was investigated onto different Michael acceptors [ 7 ]. The reaction of dienones such as 6 (Miginiac) [ 8 ], enynones of the type 8 (Hulce) [ 9 ] or polarized enynes 10 (Krause) [ 10 ] consistently proceeded with a 1,6-selectivity, as compounds 7 , 9 and 11 were respectively identified as the major reaction product. The selective 1,6-addition of cuprates onto extended Michael acceptors featuring a terminal C–C triple bond prompted research groups to investigate thoroughly the mechanism of this reaction [ 11 – 13 ].…”

Section: Reviewmentioning

confidence: 99%

Copper-catalyzed asymmetric conjugate addition of organometallic reagents to extended Michael acceptors

Schmid¹,

Drissi-Amraoui²,

Crévisy³

et al. 2015

Beilstein J. Org. Chem.

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SummaryThe copper-catalyzed asymmetric conjugate addition (ACA) of nucleophiles onto polyenic Michael acceptors represents an attractive and powerful methodology for the synthesis of relevant chiral molecules, as it enables in a straightforward manner the sequential generation of two or more stereogenic centers. In the last decade, various chiral copper-based catalysts were evaluated in combination with different nucleophiles and Michael acceptors, and have unambiguously demonstrated their usefulness in the control of the regio- and enantioselectivity of the addition. The aim of this review is to report recent breakthroughs achieved in this challenging field.

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1,4-Addition of grignard reagents and 1,6-addition of lithium organocuprates to n,n-diethylsorbamide

Cited by 30 publications

References 7 publications

Catalytic Regio‐ and Enantioselective Alkylation of Conjugated Dienyl Amides

Catalytic Regio‐ and Enantioselective Alkylation of Conjugated Dienyl Amides

Conjugate addition reactions of carbon nucleophiles to electron-deficient dienes

Copper-catalyzed asymmetric conjugate addition of organometallic reagents to extended Michael acceptors

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