Reaction of the π-allyl groups of the dodecatrienylnickel complex with aldehydes, acetyl chloride, and allyl bromide

Baker, R.; Blackett, B. N.; Cookson, R. C.; Cross, R. C.; Madden, D. P.

doi:10.1039/c39720000343

Cited by 10 publications

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“…These two characteristics combine to bestow Ni(0) complexes with catalytic activities that promote the dimerization-allylation of aldehydes with dienes. The results of the reaction between acetaldehyde and 1,3-butadiene in the presence of phosphine ligands are shown in Table 5.1 [21,22]. In general, four types of isomers, composed of two trienyl alcohols 5.8a,b and two dienyl alcohols 5.8c,d, are formed.…”

Section: 14mentioning

confidence: 99%

Reaction of Dienes and Allenes

Kimura

Tamaru

2005

Modern Organonickel Chemistry

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1,3-Butadiene and isoprene (2-methyl-1,3-butadiene) are among the most important building blocks both in the laboratory and in the chemical industry. 1,3-Butadiene (DH f ¼ þ26:1) and 1,2-butadiene (methylallene DH f ¼ þ38:8) are highly unsaturated and labile even toward relatively unreactive reagents, such as O 2 in air, and undergo polymerization during storage.Although the [4þ2]cycloaddition -the so-called Diels-Alder reaction -of butadiene to afford 4-vinylcyclohexene is a thermally permitted process, it only proceeds under harsh conditions (e.g., at 250 C under high pressure). In contrast, nickel complexes promote the [4þ2]cycloaddition under milder conditions (e.g., at 0 C under ambient pressure) [1]. Furthermore, the complexes even promote thermally forbidden [4þ4]cycloaddition and other reactions. Many other 1,3-dienes and allenes are also subject to dimerization, oligomerization, and polymerization under nickel catalysis, and hence serve as useful C4 and C3 carbon resources for a variety of organic syntheses.This chapter deals with recent developments in the nickel-catalyzed functionalizations of conjugated dienes and allenes, and incorporates the following topics: 1) dimerization and polymerization; 2) allylic and homoallylic alkylation of carbonyl compounds (dienes and allenes as nucleophiles); and 3) 1,2-and 1,4-addition reactions of reagents X-Y toward dienes and allenes. 5.1Dimerization and Polymerization of 1,3-Dienes Nickel complexes are extremely effective catalysts for the dimerization and polymerization of dienes. The catalytic reactions are described in Chapter 6, Section 6.4. The major subject of this section relates to the structures and reactivities of Ni(II)Á(butadiene) 2 complexes (the stoichiometric reactions) and recent developments in the field of polymerization.Modern Organonickel Chemistry. Edited by Y. Tamaru

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Section: 14mentioning

confidence: 99%

Reaction of Dienes and Allenes

Kimura

Tamaru

2005

Modern Organonickel Chemistry

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“…For example, the main product of the reaction of [Ni(^3,r; 3 -Ci2Hi8)] with allyl bromide is the pentaene (1) (equation 12), 74 while the product of the reaction of [Ni(PPh 3 )(77 3 ,?7 3 -C 8 Hi2)] with carbon monoxide is vinylcyclohexene, which is also formed in the intramolecular dehalogenation of (BrCH 2 CH=CHCH 2 ) 2 in DMF (equation 13) (see ref. DMF (equation 11; see also Section 37.6.2), it is perhaps mechanistically relevant that the resulting bis(?7 3 -allyl)nickel complexes react readily with organic halides as well as undergoing reductive coupling in the presence of donors.…”

Section: Reactions Involving Allylic Halidesmentioning

confidence: 99%