Unconventional Cyclometalation Reactions

Cyclometalation reactions are usually defined as the reactions of metal compounds with conventional substrates, such as benzylamines and 2-phenylpyridines. In contrast, unconventional cyclometalation reactions are the reactions of metal compounds with unconventional base substrates, such as 2-amino-3-picoline, anilines and 2- aminopyridines, and with auxiliary substrates, such as aldehydes and alkynes. Other unconventional cyclometalation reactions also exist, examples include the cyclocarbonylations of metal carbonyl compounds with unsaturated hydrocarbons, such as alkynes, alkenes and aryl compounds; reactions with 2-vinylpyridines; and rollover cyclometalation reactions.