The interplay of carbophilic activation and Au(i)/Au(iii) catalysis: an emerging technique for 1,2-difunctionalization of C–C multiple bonds

Abstract

This review highlights a decade-long journey of Au-catalyzed 1,2-difunctionalization reactions of C–C multiple bonds that have been realized due to the productive integration of Au(i)/Au(iii)catalysis with unique π-activation mode of gold complexes.

Chiral Hemilabile P,N‐Ligand‐Assisted Gold Redox Catalysis for Enantioselective Alkene Aminoarylation

“…As the catalytic cycle involves both Au I and Au III intermediates, it is plausible to achieve enantioselective gold redox catalysis with better stereochemistry control through the following two‐step sequences: A) apply stable chiral Au I complexes as catalyst resting state and B) control reaction stereochemistry at the Au III intermediates formed in situ. Therefore, the stereo‐determining step (SDS) would be set at the four coordinated Au III stage with improved spatial control (Scheme 1A) [9] . Based on this concept, in this work, we report the application of chiral hemilabile P,N ligands to achieve enantioselective alkene arylamination through gold redox catalysis.…”

Transition-metal-catalyzed C–H bond alkylation using olefins: recent advances and mechanistic aspects

“…[1][2][3][4][5][6][7][8][9][10][11] Within the domain, transition metal catalysis forms the largest, ever expanding subset contributing to the broad spectrum of applications that ranges from organic synthesis to petrochemical processing. [12][13][14][15][16][17][18][19][20] In this context, the development of novel methods to access arylation, [21][22][23][24] alkenylation [25][26][27] and alkynylation of C-H bonds 28 has gained tremendous attention. In comparison, alkylative C-H functionalizations have remained fairly scarce in the realm of transition metal catalysis due to the inert nature of the C-H bond, the large kinetic barrier for the C-H bond cleavage and its ubiquitous nature.…”

Ligand-enabled oxidation of gold(i) complexes with o-quinones

“…Au(I)/Au(III) redox cycles also open new avenues in gold catalysis, and major achievements have been reported recently in cross-coupling and alkene difunctionalization reactions in particular. 1,7 To develop this chemistry further, it is highly desirable to identify and study new routes to cycle between Au(I) and Au(III). In this context, we questioned here the possibility to use obenzoquinones to oxidize Au(I) complexes and obtain catecholate Au(III) complexes.…”