title: Enantioselective lithiation of O-alkyl and O-alk-2-enyl Carbamates in the presence of (-)-sparteine and (-)-alpha-isosparteine. A theoretical study.
abstract: Quantum chemical DFT calculations at the B3LYP/6-31G(d) level have been used to study the enantioselective lithiation/deprotonation of O-alkyl and O-alk-2-enyl carbamates in the presence of (-)-sparteine and (-)-alpha-isosparteine. Complete geometry optimization of the precomplexes consisting of the carbamate, the chiral ligand, and the base (iPrLi), for the transition states of the proton-transfer reaction, and for the resulting lithio carbamates have been performed in order to quantify activation barriers and reaction energies. For the lithiodeprotonation of ethyl carbamate 12 in the presence of (-)-sparteine (5) the preferred abstraction of the pro-S proton (by 2.75 kcal/mol) gives the (S)-lithio derivate (S)-14, which is in good agreement with experimental observations. (-)-alpha-Isosparteine (6) is predicted to be significantly less selective favoring the abstraction of the pro-R proton by 1.2 kcal/mol. The O-alkenyl carbamate 17 as an example of an allylic carbamate is more easily lithiated than 12. As for 12 (-)-sparteine (5) favors the abstraction of the pro-S proton, although with smaller preference (0.7 kcal/mol). Structural parameters are discussed to rationalize the theoretical results.
authors.affiliation: Organisch-Chemisches Institut der Westfälischen Wilhelms-Universität Münster, Corrensstrasse 40, D-48149 Münster, Germany. wurthwe@uni-muenster.de
authors.forename: Ernst-Ulrich
authors.initials: EU
authors.lastname: Würthwein
authors.forename: Dieter
authors.initials: D
authors.lastname: Hoppe
mesh_terms: D002219:Carbamates / Q000737:chemistry*; D008094:Lithium / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D013034:Sparteine / Q000737:chemistry*; D013237:Stereoisomerism; D013816:Thermodynamics
chemical_list: D002219:Carbamates; D009942:Organometallic Compounds; D013034:Sparteine; D008094:Lithium