General Methods. Reactions were performed under a nitrogen atmosphere employing standard Schlenk and/or drybox techniques unless specified otherwise. NMR were obtained on a Varian spectrometer operating at 400 MHz for 1 H, 202 MHz for 31 P, and 100 MHz for 13 C in CDCl 3 at 25 ¡C unless stated otherwise. IR spectra were obtained on a Nicolet Avatar 360-FT IR spectrometer. Gas chromatography was performed on a HP 5890 gas chromatograph equipped with a 25 m polydimethylsiloxane capillary column. Column chromatography was performed employing 230-450 mesh silica gel (Sorbent Technologies) unless noted otherwise; alternatively, chromatography employed 150 mesh activated aluminum oxide, neutral, Brockmann I (Aldrich). Thin layer chromatography (TLC) was performed on silica gel 60 F 254 . All compounds were isolated as colorless oils unless noted otherwise. Elemental analyses were performed by Complete Analysis Laboratories (Parsippany, NJ).1,4-Dioxane (anhydrous, Acros), triphenylphosphine (Fluka), and [PtCl 2 (C 2 H 4 )] 2(2) (Strem) were used as received. Tetrahydrofuran (THF) and diethyl ether were distilled from Na 0 /benzoquinone under N 2 , dichloromethane was distilled from CaH 2 under N 2 , and dioxane-d 8 was distilled from Na/K alloy under vacuum. [PtCl 2 (PPh 3 )] 2 (4) was synthesized employing a published procedure. S1 All other reagents were purchased from major chemical suppliers and were used as received.

Reaction of benzyl (2,2-diphenyl-4,5-hexadienyl)carbamate (4) with a catalytic 1:1 mixture of Au[P(t-Bu)2(o-biphenyl)]Cl (2) and AgOTf (5 mol %) in dioxane at 25 degrees C for 45 min led to isolation of benzyl 4,4-diphenyl-2-vinylpyrrolidine-1-carboxylate (5) in 95% yield. The Au(I)-catalyzed intramolecular hydroamination of N-allenyl carbamates tolerated substitution at the alkyl and allenyl carbon atoms and was effective for the formation of piperidine derivatives. gamma-Hydroxy and delta-hydroxy allenes also underwent Au-catalyzed intramolecular hydroalkoxylation within minutes at room temperature to form the corresponding oxygen heterocycles in good yield with high exo-selectivity. 2-Allenyl indoles underwent Au-catalyzed intramolecular hydroarylation within minutes at room temperature to form 4-vinyl tetrahydrocarbazoles in good yield. Au-catalyzed cyclization of N-allenyl carbamates, allenyl alcohols, and 2-allenyl indoles that possessed an axially chiral allenyl moiety occurred with transfer of chirality from the allenyl moiety to the newly formed stereogenic tetrahedral carbon atom.

The development of general and efficient methods for the addition of an N–H bond across a C–C multiple bond (hydroamination) represents a significant challenge in both organic synthesis and homogeneous catalysis. Although a diverse range of transition‐metal complexes have been employed as catalysts for hydroamination, examples of gold‐catalyzed hydroamination were exceedingly rare prior to 2001. However, over the past five years gold complexes have been applied as catalysts for a number of selective organic transformations including the hydroamination of unactivated alkenes, alkynes, allenes, and 1,3‐dienes. This Microreview provides a brief overview of the gold‐catalyzed hydroamination of C–C multiple bonds. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

The use of gold(I) complexes as catalysts for organic transformations has become increasingly common over the past decade, leading to the development of a number of useful carbon-carbon and carbon-heteroatom bond-forming processes. In contrast, enantioselective catalysis employing gold(I) complexes was, until recently, exceedingly rare, due in large part to the pronounced tendency of gold(I) to form linear, two-coordinate complexes. However, new approaches and strategies have emerged over the past two years, leading to the development of a number of effective gold(I)-catalyzed enantioselective transformations, most notably the enantioselective hydrofunctionalization of allenes. Outlined herein is an overview of enantioselective gold(I) catalysis since 2005.