PMID: 11925250Apr 2, 2002Paper

Highly diastereoselective aziridination of imines with trimethylsilyldiazomethane. Subsequent silyl substitution with electrophiles, ring opening, and metalation of C-silylaziridines--a cornucopia of highly selective transformations

The Journal of Organic Chemistry
Varinder K AggarwalSharon E Spey

Abstract

Treatment of a range of N-sulfonyl (Ts and SES) imines derived from aromatic, heteroaromatic, aliphatic, and unsaturated aldehydes with trimethylsilydiazomethane gave C-silylaziridines in good yield (32-83%) and with high diastereoselectivity in favor of the cis product (80:20-100:0). In contrast, an alpha-imino ester gave predominantly the trans-aziridine (89:11) in high yield (91%). The synthetic potential of C-silylaziridines was investigated. Treatment with F(-) (tetrabutylammonium triphenyldifluorosilicate was used) in the presence of aldehydes gave the alpha-hydroxyaziridines in high yield and high diastereoselectivity (86:14-98:2) for the newly created stereogenic center. Complete retention of configuration was observed in the substitution of the silyl group with electrophiles in all cases. Trapping with deuterium (using CDCl(3) as electrophile) was also successful, but trapping with phosphate [using ClP(O)(OPh)(2)] and acetate (using Ac(2)O) was unsuccessful. In these latter cases ring opening by chloride and acetate, respectively, was observed. Further ring-opening reactions were effected using azide and thiolate nucleophiles and in all cases complete regioselectivity in favor of attack at the silyl-bearing carbon occu...Continue Reading

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Citations

Mar 12, 2005·Chemistry : a European Journal·Antonio Morán RamallalJavier González
Mar 30, 2007·Chemical Communications : Chem Comm·Tamara L ChurchGeoffrey W Coates
May 23, 2017·Organic & Biomolecular Chemistry·Nicola PiensMatthias D'hooghe
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May 18, 2010·Chemical Reviews·Saverio Florio, Renzo Luisi
Aug 31, 2019·The Journal of Organic Chemistry·Shuqi ChenDingqiao Yang
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Aug 5, 2003·The Journal of Organic Chemistry·José M Concellón, Estela Riego

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