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Synfacts 2016; 12(05): 0484
DOI: 10.1055/s-0035-1562065
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

Iridium-Catalyzed Asymmetric Hydroxymethylation

Contributor(s):
Hisashi Yamamoto
,
Sukalyan Bhadra
Garza VJ, Krische MJ * University of Texas at Austin, USA
Hydroxymethylation beyond Carbonylation: Enantioselective Iridium-Catalyzed Reductive Coupling of Formaldehyde with Allylic Acetates via Enantiotopic π-Facial Discrimination.

J. Am. Chem. Soc. 2016;
138: 3655-3658
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Further Information

Publication History

Publication Date:
18 April 2016 (online)

 
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Key words

asymmetric catalysis - hydroxymethylation - reductive coupling - paraformaldehyde - allylic acetates - iridium

Significance

Existing examples of enantioselective C–C coupling reactions of formaldehyde involve asymmetric aldol reactions. Krische and Garza describe the first asymmetric nucleophilic allylation of formaldehyde in the presence of iridium catalysts to give chiral β-stereogenic primary homoallylic alcohols.


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Comment

The chiral iridium complex modified by SEGPHOS permits propan-2-ol-mediated regio- and enantioselective reductive coupling of branched allylic acetates with paraformaldehyde. The reaction proceeds through formation of an iridium hydride and subsequent formation of π-allyliridium intermediates.


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