Scaleable Preparation of Functionalized Organometallics via Directed Ortho Metalation Using Mg- and Zn-Amide Bases

Autor:	Christoph J. Rohbogner, Paul Knochel, Andreas Unsinn, Stefan H. Wunderlich
Rok vydání:	2010
Předmět:	chemistry.chemical_compound Aqueous solution chemistry Metalation Amide Aryl Organic Chemistry Electrophile Organic chemistry Physical and Theoretical Chemistry Medicinal chemistry Directed ortho metalation Group 2 organometallic chemistry
Zdroj:	Organic Process Research & Development. 14:339-345
ISSN:	1520-586X 1083-6160
DOI:	10.1021/op9002888
Popis:	A range of aryl and heteroaryl organometallics are efficiently prepared in THF via directed ortho metalation by using the previously reported amide bases tmpMgCl·LiCl (tmp = 2,2,6,6-tetramethylpiperidyl), tmp2Mg·2LiCl and tmp2Zn·2MgCl2·2LiCl. These metalation reactions are carried out at 80−100 mmol scale. The unsaturated organometallic compounds undergo smooth reactions with various electrophiles, e.g. additions to carbonyl groups, Pd-catalyzed cross-coupling reactions or Cu-catalyzed acylations. In all cases, the metalation rates have been compared with corresponding small-scale reactions (1−2 mmol). Moreover, a procedure for the recovery of the valuable tmp-H from the aqueous layer is reported.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::29e02f623611bce5c92d9bcd52e62dc5 https://doi.org/10.1021/op9002888 Zobrazit plný text záznamu