Novel and Highly Regio- and Stereoselective Nickel-Catalyzed Homoallylation of Benzaldehyde with 1,3-Dienes

Kimura, Masanari; Ezoe, Akihiro; Shibata, Kazufumi; Tamaru, Yoshinao

doi:10.1021/ja973847c

Cited by 172 publications

(52 citation statements)

References 7 publications

(9 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The first intermolecular metal-catalyzed reductive coupling of dienes with carbonyl compounds, a process mediated by triethylborane, was reported by Kimura and Tamaru in 1998 (19, 20) (Figure 5). Diverse dienes may be converted to the respective homoallylation products in good yields and excellent levels of anti -1,3-diastereoselectivity.…”

Section: Dienes and Enynesmentioning

confidence: 94%

See 1 more Smart Citation

Metal-catalyzed reductive coupling of olefin-derived nucleophiles: Reinventing carbonyl addition

Nguyen

Park

Luong

et al. 2016

Science

302

120

View full text Add to dashboard Cite

α-Olefins are the most abundant petrochemical feedstock beyond alkanes, yet their use in commodity chemical manufacture is largely focused on polymerization and hydroformylation. The development of byproduct-free catalytic C-C bond forming reactions that convert olefins to value-added products remains an important objective. Here, we review catalytic intermolecular reductive couplings of unactivated and activated olefin-derived nucleophiles with carbonyl partners. These processes represent an alternative to the longstanding use of stoichiometric organometallic reagents in carbonyl addition.

show abstract

Section: Dienes and Enynesmentioning

confidence: 94%

“…Regioselectivity in favor of coupling to the more substituted olefin moiety is observed. A mechanism involving diene-carbonyl oxidative coupling to form transient oxo-nickelacycles is postulated (19, 20). Corresponding ketone homoallylations were developed using diethylzinc as terminal reductant (21).…”

Section: Dienes and Enynesmentioning

confidence: 99%

Metal-catalyzed reductive coupling of olefin-derived nucleophiles: Reinventing carbonyl addition

Nguyen

Park

Luong

et al. 2016

Science

302

120

View full text Add to dashboard Cite

show abstract

“…[15,16] In related mechanistic studies by Ogoshi,[17a] the stoichiometric reaction of nickel(0) with 2-substituted dienes and aldehydes provided isolable metallacycles. Here, metallacycle formation was demonstrated to be reversible, and it was shown that for the formation of the C1 adducts, oxidative coupling was kinetically preferred.…”

Section: Diene Hydrohydroxymethylationmentioning

confidence: 99%

Paraformaldehyde and Methanol as C₁ Feedstocks in Metal‐Catalyzed CC Couplings of π‐Unsaturated Reactants: Beyond Hydroformylation

2014

View full text Add to dashboard Cite

Ruthenium-catalyzed reductive couplings of paraformaldehyde with dienes, alkynes, and allenes provide access to products of hydrohydroxymethylation that cannot be formed selectively under the conditions of hydroformylation. In certain cases, the regioselectivity of the CC coupling can be inverted by using nickel catalysts. With iridium catalysts, methanol engages in redox-neutral regioselective hydrohydroxymethylations.

show abstract

“…Recently, 1,3-dienes were shown to serve as homoallyl anion equivalents and to react with aromatic aldehydes in the presence of a catalytic amount of Ni(acac) 2 and a stoichiometric amount of Et 3 B at room temperature to provide 1-aryl-4-pentenols 5.20 (Table 5.2) [38]. The reaction proceeds with high regio-and stereoselectivities, selectively yielding a 1:1 adduct of diene and aldehyde.…”

Section: Homoallylation Of Aldehydes Promoted By Triethylborane or DImentioning

confidence: 99%

Reaction of Dienes and Allenes

Kimura

Tamaru

2005

Modern Organonickel Chemistry

Self Cite

View full text Add to dashboard Cite

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

show abstract

Novel and Highly Regio- and Stereoselective Nickel-Catalyzed Homoallylation of Benzaldehyde with 1,3-Dienes

Cited by 172 publications

References 7 publications

Metal-catalyzed reductive coupling of olefin-derived nucleophiles: Reinventing carbonyl addition

Metal-catalyzed reductive coupling of olefin-derived nucleophiles: Reinventing carbonyl addition

Paraformaldehyde and Methanol as C₁ Feedstocks in Metal‐Catalyzed CC Couplings of π‐Unsaturated Reactants: Beyond Hydroformylation

Reaction of Dienes and Allenes

Contact Info

Product

Resources

About

Novel and Highly Regio- and Stereoselective Nickel-Catalyzed Homoallylation of Benzaldehyde with 1,3-Dienes

Cited by 172 publications

References 7 publications

Metal-catalyzed reductive coupling of olefin-derived nucleophiles: Reinventing carbonyl addition

Metal-catalyzed reductive coupling of olefin-derived nucleophiles: Reinventing carbonyl addition

Paraformaldehyde and Methanol as C1 Feedstocks in Metal‐Catalyzed CC Couplings of π‐Unsaturated Reactants: Beyond Hydroformylation

Reaction of Dienes and Allenes

Contact Info

Product

Resources

About

Paraformaldehyde and Methanol as C₁ Feedstocks in Metal‐Catalyzed CC Couplings of π‐Unsaturated Reactants: Beyond Hydroformylation