Difunctionalization of Alkenes Involving Metal Migration

Abstract

The direct difunctionalization of alkenes, a cheap and abundant feedstock, represents one of the most attractive strategies for increasing molecular complexity in synthetic organic chemistry. In contrast with the 1,2‐difunctionalization of alkenes, recent advances showcase alkene 1,n‐difunctionalizations (n≠2) involving metal migration is an emerging and rapidly growing area of research. This promising strategy not only opens a novel avenue for future development of alkene transformations, but also significantly expands upon the bond disconnections available in modern organic synthesis. This Minireview summarizes recent progress in the migratory difunctionalization of alkenes, with an emphasis on the driving force for metal migration.

Metal-free, visible-light induced enantioselective three-component dicarbofunctionalization and oxytrifluoromethylation of enaminesviachiral phosphoric acid catalysis

“…Multi-component difunctionalization of alkenes offers a simple and efficient strategy for the synthesis of complex compounds, which allows for the simultaneous construction of two C–X bonds in one-step from readily available alkenes and other starting materials. 1,2 Due to the high reactivity and unique philicity, radical species have been extensively investigated in the asymmetric difunctionalization of alkenes via transition metal catalysis. 3 Recently, Liu's group 4 developed a dual Cu( i )/CPAs catalysis strategy for the asymmetric dicarbofunctionalization of 1,1-diarylalkenes, which proceeded via a radical generation and single-electron oxidation step catalyzed by copper( i ) and enantioselective nucleophilic attack step catalyzed by CPAs ( Scheme 1a ).…”

Photoredox-catalyzed aminofluorosulfonylation of unactivated olefins

“…The direct difunctionalization of alkenes is a powerful strategy for the rapid assembly of molecular complexity and diversity. 8 With our continuous research interest in sulfonyl fluoride synthesis, 5 a ,9 we intended to achieve the radical 1,2-difunctionalization of unactivated alkenes providing functionalized aliphatic sulfonyl fluoride derivatives. To the best of our knowledge, the sole example so far is fluoroalkylation–fluorosulfonylation of alkenes recently developed by the group of Liu and Chen.…”

Computational mechanistic studies of the carbon–carbon double bond difunctionalization via epoxidation and subsequent aminolysis in vegetable oils

“…The CC double bond is very important in synthetic applications because of its reactivity [1]. CC bond bearing compounds can act as building blocks for several functionalities such as amines, alcohols, aldehydes, epoxides, or acids [2–4]. Naturally available and low‐cost CC bond containing substances can act as an alternative to fossil fuels: Among vegetable oils, soybean oil, in particular, contains roughly 60 wt% linoleic acid, and a total of 80 wt% unsaturated residues, which makes it more modifiable and eventually more applicable compared to other vegetable oils.…”