Facile and Highly Diastereoselective Synthesis of syn- and cis-1,2-Diol Derivatives from Protected alpha-Hydroxy Ketones

0454233 - ÚOCHB 2016 RIV DE eng J - Článek v odborném periodiku
Jahn, Emanuela - Smrček, Jakub - Pohl, Radek - Císařová, I. - Jones, P. G. - Jahn, Ullrich
Facile and Highly Diastereoselective Synthesis of syn- and cis-1,2-Diol Derivatives from Protected alpha-Hydroxy Ketones.
European Journal of Organic Chemistry. Roč. 2015, č. 35 (2015), s. 7785-7798. ISSN 1434-193X. E-ISSN 1099-0690
Grant ostatní: COST(XE) CM1201
Institucionální podpora: RVO:61388963
Klíčová slova: synthetic methods * reduction * diastereoselectivity * diols * ketones
Kód oboru RIV: CC - Organická chemie
Impakt faktor: 3.068, rok: 2015

An efficient method for the synthesis of monoprotected syn- or cis-1,2-diol derivatives by reduction of easily accessible -(2,2,6,6-tetramethylpiperidinyloxy) ketones is reported. The -(tetramethylpiperidinyloxy) group as the stereodirecting group induces in unhindered acyclic or cyclic ketones complete syn- or cis-diastereoselectivity, respectively, with L-Selectride. For more hindered derivatives, where L-Selectride becomes unreactive, LiAlH4 proved effective, essentially showing the same high selectivity. The diastereoselectivity of the reduction can be rationalized for acyclic ketones by the Felkin-Anh model, whereas for cyclic substrates, attack from the face opposite to the tetramethylpiperidinyloxy group predictably prevails with high selectivity regardless of the substitution pattern. The liberation of free diols was achieved by reductive N-O bond cleavage of the alkoxyamine unit.
Trvalý link: http://hdl.handle.net/11104/0254939