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High Chelation Control of Three Contiguous Stereogenic Centers in the Reformatsky Reactions of Indium Enolates with α-Hydroxy Ketones:  Unexpected Stereochemistry of Lactone Formation

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journal contribution
posted on 06.07.2006, 00:00 by Srinivasarao Arulananda Babu, Makoto Yasuda, Yuji Okabe, Ikuya Shibata, Akio Baba
A boat-type of chelated bicyclic transition state involving highly diastereoselective construction of three contiguous stereogenic centers in the Reformatsky reaction of indium enolates with α-alkoxy/hydroxy ketones is proposed. α-Hydroxy ketones with indium enolates furnished highly diastereoselective lactones, while α-alkoxy ketones gave acyclic esters in moderate selectivities. X-ray structure analyses of key products unequivocally revealed the unexpected stereochemistry of products and the reaction pathway.