Nickel‐Catalyzed Coupling of Carbonyl Compounds and Alkynes or 1,3‐Dienes: An Efficient Method for the Preparation of Allylic, Homoallylic, and Bishomoallylic Alcohols

Abstract

Nickel‐catalyzed multicomponent coupling of carbonyl compounds with alkynes or 1,3‐dienes and organometallic reagents represents an efficient route to allylic, homoallylic, and bishomoallylic alcohols with good regio‐, stereo‐, and enantioselectivity. The reaction proceeds via the nickelacycle species I or I′ (see scheme), and not by the usual alkenylation, allylation, and homoallylation of carbonyl compounds.

Highly Efficient Chemical Kinetic Resolution of Bishomoallylic Alcohols: Synthesis of (R)-Sulcatol

“…Optically active allylic, homoallylic, and bishomoallylic alcohols are valuable intermediates in organic synthesis. The versatile transformation of their alkenyl functionality provides access to a variety of enantiomerically enriched compounds .…”

Metal‐Catalyzed Multicomponent Reactions

“…These studies were particularly focussed on the synthesis of tamoxifen-like olefins 20 as potential anti-breast-cancer drugs. The regioselectivity of the carbomagnesation has been controlled either via formation of a magnesium chelate intermediate 18 (Fallis' approach) Nickel-catalyzed intermolecular cascade reactions based notably on coupling reactions of carbonyl compounds with alkynes [22,23,36] or 1,3-dienes [37,38] have also been investigated in the search for new multicomponent coupling processes. Ikeda and Sato have discovered that enones couple with alkynes in the presence of TMSCl and catalytic amounts of Ni(0) to form an alkenylnickel intermediate 21.…”

Catalytic Carbonyl Z-Dienylation via Multicomponent Reductive Coupling of Acetylene to Aldehydes and α-Ketoesters Mediated by Hydrogen: Carbonyl Insertion into Cationic Rhodacyclopentadienes

“…Moreover, to achieve broadest impact, hydrogen-mediated C−C coupling should be applicable to basic chemical feedstocks. Acetylene is vastly abundant (2 cents/mol, annual U.S. production >500 metric kilotons), yet this important feedstock has not been exploited in catalytic reductive couplings to carbonyl compounds. − Here, we report that exposure of aldehydes and ketones to equal volumes of acetylene and hydrogen gas at ambient temperature and pressure in the presence of cationic rhodium catalysts provides products of carbonyl Z -dienylation 6n. In this multicomponent coupling, four molecules are combined: two molecules of acetylene, a molecule of carbonyl compound, and elemental hydrogen.…”