Transition‐Metal‐Catalyzed Three‐Component Difunctionalizations of Alkenes

Abstract

Three-component reactions can directly convert three reactants into the desired products in one pot and thus greatly shorten the synthetic path. Recently, transition-metal catalysis has been applied in the difunctionalization of alkenes and remarkable progress has been achieved to facilitate the construction of a wide range of functional molecules with high atom- and step-economic efficiency. This Focus Review highlights recent advances in this field.

Synthesis of 2‐Aryl‐2‐hydroxyethyl Dithiocarbamates via Regioselective Addition of Tetraalkylthiuram Disulfides to Styrenes under Transition‐Metal‐Free Conditions

“…Transition‐metal‐catalyzed difunctionalization of alkenes is a powerful method for the introduction of two functional groups into an alkene in a one‐step manner, having advantages such as high efficiency, excellent regioselectivity and good functional group tolerance [1] . Over the past decades, extensive developments have been achieved with transition‐metal‐catalyzed protocols (such as copper, [1h–j,2] palladium, [1a,c,3] nickel, [4] gold, [5] rhodium, [6] iron, [7] silver, [8] cobalt, [9] manganese, [10] and other metals [11] ). However, the use of transition metals may lead to potential contamination of the products, which is particularly significant in the pharmaceutical industry.…”

Four‐Component Borocarbonylation of Vinylarenes Enabled by Cooperative Cu/Pd Catalysis: Access to β‐Boryl Ketones and β‐Boryl Vinyl Esters

“…[1] Among these methods,t ransition-metal-catalyzed olefin difunctionalization represents an efficient strategy that allows two functional groups appended to the double bond in one step,thus enabling the rapidly assembly of molecular complexity. [2] On the other hand, organoboranes served as significant synthetic intermediates in organic transformations and were also employed in the synthesis of various natural products and bioactive molecules. [3] Concerning their preparation, the 1,2-carboboration of olefins offers astraightforward approach to access highly functionalized organoboranes.…”

Nickel‐CatalyzedDicarbofunctionalization of Alkenes†

“…[ 1‐7 ] Among the developed methods, transition metal‐catalyzed difunctionalization of alkenes enables preparation of complex molecules from simple available alkenes by diversifying the C=C double bond with high atom‐ and step‐economic efficiency. [ 8‐21 ] In particular, the dicarbofunctionalization of alkenes has gained special attention because it can construct complex carbon skeletons by assembling two carbon entities across the C=C bond and forming two C—C bonds in an one‐pot reaction (Scheme 1). [ 22‐25 ] Over the past decade, considerable efforts have been devoted to this area and impressive progress has been achieved.…”