Masanari Kimura

Pd·Et3B-catalyzed alkylation of amines with allylic alcoholsElectronic supplementary information (ESI) available: experimental section. See http://www.rsc.org/suppdata/cc/b2/b210920d/

A combination of catalytic amounts of Pd (0.05 mmol) and Et3B (0.3 mmol) promotes allylic alkylation of primary and secondary aromatic and aliphatic amines (1.0 mmol) by the direct use of allylic alcohols, providing tertiary amines in excellent yields under mild conditions (room temperature approximately 50 degrees C).

Et3B-promoted, Pd(0)-catalyzed allylation of active methylene compounds with allylic alcohols

Abstract Triethylborane promotes the Pd(0)-catalyzed allylation of active methylene compounds (Meldrum’s acid and malonates) with a variety of allylic alcohols. The reaction proceeds smoothly at room temperature and provides the allylation products in good yield.

Et3B–Pd-promoted allylation of benzaldehyde with allylic alcohols

In the presence of Pd(OAc)2 (0.05 equiv.) and PPh3 (0.1 equiv.), triethylborane promotes a variety of allyl alcohols to undergo allylation of benzaldehyde to provide homoallyl alcohols in good yield.

Et 3 B-promoted, Pd-catalyzed C -allylation of o -hydroxyacetophenone and its derivatives with allyl alcohols

Triethylborane promotes the Pd-catalyzed selective C-diallylation of o-hydroxyacetophenone and C-monoallylation of o-hydroxypropiophenone with a variety of ally alcohols. The reaction proceeds smoothly at 25–50°C and provides the allylation products in excellent yields.

Convenient synthesis of densely functionalized N-substituted 4-methylene-2-oxazolidinone

Abstract O-Propargyl carbamates 1 undergo an intramolecular nucleophilic addition to acetylenic bond at the nitrogen atom to furnish 4-methylene-2-oxazolidinones 2 in good yields in the presence (Cu + for R 1 = p -toluenesulfonyl, Ag + for R 1 = acyl) or absence (for R 1 = alkyl and aryl) of a transition metal catalyst.

Nickel(0)-Catalyzed Three-Component Connection Reaction of Dimethylzinc, 1,3-Dienes, and Carbonyl Compounds.

Linear 1:1:1 coupling of dimethylzinc, 1,3-dienes, and carbonyl compounds in this order is facilitated by catalytic amounts of [Ni(acac)(2)] to give (E)-3-hexen-1-ols in good yields under mild conditions [Eq. (a)]. Increasing steric hindrance at the carbonyl group favors formation of the 1:2:1 adduct, and this is the sole product when the carbonyl compound is acetone. acac=acetylacetonate.

Palladium(II)-catalyzed oxidative aminocarbonylation of unsaturated carbamates

Abstract N -Tosyl O -2-propenyl carbamates 4 undergo aminocarbonylation to provide N -tosyl-2-oxazolidinone 4-acetic acid esters 5 by the catalysis of PdCl 2 under 1 atm of CO.

Allylation of aldehydes via Umpolung of π-allylpalladium(II) with triethylborane

Abstract Triethylborane induces allylic substrates (benzoates, phenyl ethers, benzyl ethers, but not halides) to undergo allylation of aldehydes in the presence of a catalytic amount of tetrakis(triphenylphosphine)palladium(0). The reaction proceeds via Umpolung of π-allylpalladium.

Ni0-catalyzed regio- and stereoselective coupling reaction of Me3B, isoprene, and aldehydes

Abstract In the presence of Ni(acac) 2 (0.1 equiv.), the three components of trimethylborane, isoprene, and aromatic and aliphatic aldehydes combine to produce 1-substituted 3-methyl-3-hexenols ( 3 ) in good yield and with high regio- and stereoselectivity ( E : Z >13:1).

Nickel-Catalyzed Reductive Coupling of Dienes and Carbonyl Compounds

Nickel-catalyzed allylation and homoallylation of carbonyl compounds with conjugated dienes promoted by a several kind of organometallic reagents are described. In the presence of Ni(cod)2, trialkylsilanes (R3SiH) serve as reducing agents and promote ω-dienyl aldehydes to undergo intramolecular allylation with high regio- and stereoselectivity. In the presence of indium(I) iodide, Ni(acac)2 catalyzes double allylation of aldehydes with 1,3-butadiene to provide 3-hexene-1,6-diols and/or 2-vinyl-1,4-butanediols. The combination of Ni(acac)2 and triethylborane selectively promotes homoallylation of aromatic aldehydes and α,β-unsaturated aldehydes. The reaction shows high regio- and stereoselectivity. Isoprene, for example, provides 1-substituted 3-methyl-4-pentenols with excellent 1,3-anti stereoselectivity. Diethylzinc, in place of Et3B, nicely promotes the homoallylation of less reactive carbonyl compounds (sterically congested aliphatic aldehydes and ketones). 1,3-Cyclohexadiene is one exception among the dienes examined and undergoes allylation instead of homoallylation under the catalysis of Ni-Et2Zn. Aldimines prepared in situ from aldehydes and p-anisidine undergo homoallylation with 2-substituted-1,3-deines under Ni-Et2Zn catalysis to afford bis-homoallyl amines with excellent 1,3-syn stereoselectivity.