title: Diastereoselectivity of polar and radical couplings in electrophilic substitutions of rigid 2-lithio-N-methylpyrrolidines.
abstract: 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.
authors.affiliation: Department of Chemistry and Biochemistry, University of Arkansas, Fayetteville, AR 72701, USA. bgawley@uark.edu
authors.forename: Robert E
authors.initials: RE
authors.lastname: Gawley
authors.forename: Daniel B
authors.initials: DB
authors.lastname: Eddings
authors.forename: Marcelina
authors.initials: M
authors.lastname: Santiago
authors.forename: Davic A
authors.initials: DA
authors.lastname: Vicic
mesh_terms: D003460:Crystallization; D018360:Crystallography, X-Ray; D008094:Lithium / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D011759:Pyrrolidines / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D009942:Organometallic Compounds; D011759:Pyrrolidines; D008094:Lithium