Stereoselective quaternary center construction via atom-transfer radical cyclization using silicon tethers on acyclic precursors.
A novel strategy for the stereoselective construction of all-carbon quaternary centers on acyclic molecules using a two-step tandem process is reported. The first step involves an intramolecular and stereoselective atom transfer radical cyclization reaction from an allyl or vinyl subunit attached on a silyloxy, serving as a tether, to a tertiary radical alpha to an ester. A subsequent mild acidic elimination leads stereoselectively to a quaternary center bearing an allyl or a vinyl in high yield.
Duplessis
Martin
M
Institut de recherches cliniques de Montréal, Bio-organic Chemistry Laboratory, 110 avenue des Pins Ouest, Montréal, Québec, Canada H2W 1R7.
Waltz
Marie-Eve
ME
Bencheqroun
Mohammed
M
Cardinal-David
Benoit
B
Guindon
Yvan
Y
D000498:Allyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D003500:Cyclization; D015394:Molecular Structure; D012825:Silicon / Q000737:chemistry*; D013237:Stereoisomerism; D014753:Vinyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry
D000498:Allyl Compounds; D014753:Vinyl Compounds; D012825:Silicon