Diastereoselectivity of polar and radical couplings in electrophilic substitutions of rigid 2-lithio-N-methylpyrrolidines.
N-Methyl trans-fused perhydroisoindolines substituted with a tributylstannyl group in the 2-position have been prepared and used as precursors of the corresponding alpha-aminoorganolithiums. The steric course of the reactions of these and other conformationally rigid organolithiums with various electrophiles is summarized and compared with the steric course of the unsubstituted analogs. A mechanistic rationale for the steric course of electrophilic substitutions of these organolithiums is discussed. Pathways involving both polar electrophilic substitutions and radical couplings were observed with different electrophiles.
Gawley
Robert E
RE
Department of Chemistry and Biochemistry, University of Arkansas, Fayetteville, AR 72701, USA. bgawley@uark.edu
Eddings
Daniel B
DB
Santiago
Marcelina
M
Vicic
Davic A
DA
D003460:Crystallization; D018360:Crystallography, X-Ray; D008094:Lithium / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D011759:Pyrrolidines / Q000737:chemistry*; D013237:Stereoisomerism
D009942:Organometallic Compounds; D011759:Pyrrolidines; D008094:Lithium