Recent Advances in the Intermolecular Oxidative Difunctionalization of Alkenes

Abstract

Functionalization of alkenes has been well investigated by chemists, thus it has been extensively applied in organic synthesis and industries. In the past few decades, transition-metal, such as palladium, rhodium, gold, iridium, copper and iron, catalyzed functionalization reactions of alkenes have been significantly developed and played vital roles in synthesis. The difunctionalization of alkenes are appealing as an important alternative to the traditional approaches for the construction of useful carbon centers, particularly carbon quaternary centers, which commonly existed as structural motifs in numerous natural products, pharmaceuticals, and biologically active molecules. This account will summarize our recent advances in the intermolecular difunctionalization of alkenes, and also highlight the scope and limitations as well as the mechanisms of these difunctionalization reactions. In general, in this account the difunctionalization of alkenes starting from dicarbofunctionalization will be discussed. Then carboheterofunctionalization of alkenes will be intensively reviewed, and diheterofunctionalization will also be highlighted.

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.…”

Advances in Oxosulfonylation Reaction

“…Next year, Lu and co-workers [97] reported another method for hydroxysulfonylation of arylpropiolic acids 45a with sodium sulfinates 45b in water. Mn (OAc) 3 . 2H 2 O was used as a catalyst for this conversion.…”

“…Difunctionalization is a powerful and straightforward strategy to introduce two functional groups in a single reaction to synthesize complex molecular architectures rapidly. [1][2][3][4] Epitomized by the classical Sharpless aminohydroxylation [CÀ O/CÀ N] [5] and dihydroxylation [CÀ O/CÀ O], [6] difunctionalization process is largely utilized for the introduction of two functional groups in adjacent carbons simultaneously to build highly functionalized organic compounds. [7] Over the past few years, representative reactions include carbooxygenation [CÀ C/CÀ O], [8][9][10] oxyhalogenation [CÀ O/Chalide], [11][12][13] and dicarbofunctionalization [CÀ C/ CÀ C] [7,14] reactions have been extensively developed as a powerful method due to its ability to assemble complex skeletons rapidly.…”

“…Recently, oxo-sulfonylation of alkenes and alkynes has been extensively studied to form CÀ O and CÀ S bonds simultaneously (Scheme 2, type 3). Comparing to the traditional routes for β-ketosulfones (Scheme 2, Type 1 and 2), a number of attractive features can be envisioned of direct oxo-sulfonylation protocol (Scheme 2, Type 3): (1) the oxo-sulfonylation reaction are atom-efficient and would be by-product free; (2) alkenes and alkynes are generally easy to prepare; (3) oxygen is used as green oxidant; (4) sulfonyl sources are readily accessible as described in Scheme 3.…”

Photo-mediated selective deconstructive geminal dihalogenation of trisubstituted alkenes

“…The carbon-carbon double bond is one of the most fundamental functionalities in organic molecules. Various methods have been developed to convert alkenes to important intermediates and fine chemical products, which play vital roles in the fields of material science, biochemistry, pharmaceutical science, and the chemical industry [1][2][3][4][5][6][7][8] . Deconstructive functionalization of alkenes has been well developed to introduce two functional groups at different sites of olefins ( Fig.…”