A Tandem Iridium-Catalyzed “Chain-Walking”/Cope Rearrangement Sequence

Non-carbonyl-stabilized metallocarbenoids in synthesis: the development of a tandem rhodium-catalyzed bamford-stevens/thermal aliphatic claisen rearrangement sequence.

A tandem rhodium-catalyzed Bamford-Stevens/Claisen rearrangement is presented. The tandem reaction uses Eschenmoser hydrazones for the in situ generation of non-carbonyl-stabilized diazo alkanes, which are presumably intercepted by Rh(II) catalysts to induce a 1,2-hydride migration. This sequence provides high levels of stereocontrol for the generation of simple acyclic (Z)-enol ethers. These e...

Iridium–catalyzed 1,3–dipolar cycloadditions

1,3–Dipolar cycloaddition reactions (DCR) are atom–economic processes that permit the construction of heterocycles. Their enantioselective versions allow for the creation of up to four adjacent chiral centers in a concerted fashion. In particular, well–defined half–sandwich iridium (III) catalysts have been applied to the DCR between enals or methacrylonitrile with nitrones. Excellent yield and...

Ru-catalyzed tandem cross-metathesis/intramolecular-hydroarylation sequence.

Iridium-Catalyzed Arylative Cyclization of Alkynones by 1,4-Iridium Migration**

1,4-Metal migrations enable the remote functionalization of C-H bonds, and have been utilized in a wide variety of valuable synthetic methods. The vast majority of existing examples involve the 1,4-migration of palladium or rhodium. Herein, the stereoselective synthesis of complex polycycles by the iridium-catalyzed arylative cyclization of alkynones with arylboronic acids is described. To our ...

Iridium Complex-Catalyzed Highly Selective Organic Synthesis Iridium Complex-Catalyzed Highly Selective Organic Synthesis

Synlett 2002, No. 12, Print: 02 12 2002. Art Id.1437-2096,E;2002,0,12,1954,1965,ftx,en;A30202ST.pdf. © Georg Thieme Verlag Stuttgart · New York ISSN 0936-5214 Abstract: Two different synthetic reactions catalyzed by an iridium complex are discussed. The first is allylic alkylation and allylic amination. This reaction proceeds via a -allyl iridium intermediate. The selectivity strongly depends o...