TY - JOUR
T1 - Highly enantioselective intramolecular cyanoamidation
T2 - (+)-horsfiline, (-)-coerulescine, and (-)-esermethole
AU - Reddy, Venkata Jaganmohan
AU - Douglas, Christopher J.
PY - 2010/3/5
Y1 - 2010/3/5
N2 - (Figure Presented) The first asymmetric cyanoamidation with synthetically useful enantioselectivlty (ee up to 99%) to produce 3,3-disubstltuted oxindoles Is reported. Palladium catalysts with chi ral phosphoramldite ligands activate the cyanoformamide C-CN bond, which is subsequently functionalized with a tethered alkene to give all-carbon quaternary stereocenters. The use of the N,N-(i-Pr)2 derivative of octahydro-MonoPhos allowed the production of oxindoles with high enantioselectivlties. Cyanoformamides bearing free N-H groups are now tolerated, potentially allowing protecting-group-free synthesis. Oxindole products of cyanoamidation are rapidly transformed into (+)-horsfiline, (-)-coerulescine, and (-)-esermethole.
AB - (Figure Presented) The first asymmetric cyanoamidation with synthetically useful enantioselectivlty (ee up to 99%) to produce 3,3-disubstltuted oxindoles Is reported. Palladium catalysts with chi ral phosphoramldite ligands activate the cyanoformamide C-CN bond, which is subsequently functionalized with a tethered alkene to give all-carbon quaternary stereocenters. The use of the N,N-(i-Pr)2 derivative of octahydro-MonoPhos allowed the production of oxindoles with high enantioselectivlties. Cyanoformamides bearing free N-H groups are now tolerated, potentially allowing protecting-group-free synthesis. Oxindole products of cyanoamidation are rapidly transformed into (+)-horsfiline, (-)-coerulescine, and (-)-esermethole.
UR - http://www.scopus.com/inward/record.url?scp=77749273880&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=77749273880&partnerID=8YFLogxK
U2 - 10.1021/ol902949d
DO - 10.1021/ol902949d
M3 - Article
C2 - 20104898
AN - SCOPUS:77749273880
SN - 1523-7060
VL - 12
SP - 952
EP - 955
JO - Organic Letters
JF - Organic Letters
IS - 5
ER -