title: Stereochemical Outcomes in Reductive Cyclizations To Form Spirocyclic Heterocycles.
abstract: Reductive lithiation and cyclization of N-Boc α-amino nitriles are often highly stereoselective. The alkyllithium intermediates are formed with varying levels of selectivity, but the alkyllithium geometry does not play a major role in the overall stereoselectivity. The final configuration is determined in the cyclization reaction, where both retention and inversion pathways are observed. Where strong thermodynamic preferences exist in the products, the kinetically controlled alkyllithium cyclization favors the more stable product.
authors.affiliation: Department of Chemistry, University of California, Irvine, 1102 Natural Sciences II Irvine, California 92697, United States.
authors.forename: Matthew A
authors.initials: MA
authors.lastname: Perry
authors.affiliation: Department of Chemistry, University of California, Irvine, 1102 Natural Sciences II Irvine, California 92697, United States.
authors.forename: Richard R
authors.initials: RR
authors.lastname: Hill
authors.affiliation: Department of Chemistry, University of California, Irvine, 1102 Natural Sciences II Irvine, California 92697, United States.
authors.forename: Justin J
authors.initials: JJ
authors.lastname: Leong
authors.affiliation: Department of Chemistry, University of California, Irvine, 1102 Natural Sciences II Irvine, California 92697, United States.
authors.forename: Scott D
authors.initials: SD
authors.lastname: Rychnovsky
mesh_terms: D000478:Alkylation; D020650:Combinatorial Chemistry Techniques; D003500:Cyclization; D006574:Heterocyclic Compounds, 2-Ring / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D009570:Nitriles / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D013141:Spiro Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D013816:Thermodynamics
chemical_list: D006574:Heterocyclic Compounds, 2-Ring; D009570:Nitriles; D009942:Organometallic Compounds; D013141:Spiro Compounds