Amines bearing tertiary substituents by tandem enantioselective carbolithiation-rearrangement of vinylureas

TY - JOUR

T1 - Amines bearing tertiary substituents by tandem enantioselective carbolithiation-rearrangement of vinylureas

AU - Tait, M.

AU - Donnard, M.

AU - Minassi, A.

AU - Lefranc, J.

AU - Bechi, B.

AU - Clayden, J.

AU - Carbone, G.

AU - O'Brien, P.

PY - 2013/1/4

Y1 - 2013/1/4

N2 - In the presence of (-)-sparteine or a (+)-sparteine surrogate, organolithiums add to N-alkenyl-N'-arylureas to give benzylic organolithiums in an enantioselective manner. Under the influence of DMPU, these organolithiums undergo rearrangement with migration of the N'-aryl ring from N to C, leading to the urea derivatives of enantiomerically enriched amines bearing tertiary substituents. Basic hydrolysis returns the functionalized amine, providing a new synthetic route to compounds with quaternary stereogenic centers bearing nitrogen.

AB - In the presence of (-)-sparteine or a (+)-sparteine surrogate, organolithiums add to N-alkenyl-N'-arylureas to give benzylic organolithiums in an enantioselective manner. Under the influence of DMPU, these organolithiums undergo rearrangement with migration of the N'-aryl ring from N to C, leading to the urea derivatives of enantiomerically enriched amines bearing tertiary substituents. Basic hydrolysis returns the functionalized amine, providing a new synthetic route to compounds with quaternary stereogenic centers bearing nitrogen.

UR - http://www.scopus.com/inward/record.url?scp=84874080511&partnerID=8YFLogxK

U2 - 10.1021/ol3029324

DO - 10.1021/ol3029324

M3 - Article

AN - SCOPUS:84874080511

SN - 1523-7060

VL - 15

SP - 34

EP - 37

JO - Organic Letters

JF - Organic Letters

IS - 1

ER -