TY - JOUR
T1 - Mechanistic Complexity of Asymmetric Transfer Hydrogenation with Simple Mn-Diamine Catalysts
AU - Van Putten, Robbert
AU - Filonenko, Georgy A.
AU - Gonzalez De Castro, Angela
AU - Liu, Chong
AU - Weber, Manuela
AU - Müller, Christian
AU - Lefort, Laurent
AU - Pidko, Evgeny
PY - 2019
Y1 - 2019
N2 - The catalytic asymmetric transfer hydrogenation (ATH) of ketones is a powerful methodology for the practical and efficient installation of chiral centers. Herein, we describe the synthesis, characterization, and catalytic application of a series of manganese complexes bearing simple chiral diamine ligands. We performed an extensive experimental and computational mechanistic study and present the first detailed experimental kinetic study of Mn-catalyzed ATH. We demonstrate that conventional mechanistic approaches toward catalyst optimization fail and how apparently different precatalysts lead to identical intermediates and thus catalytic performance. Ultimately, the Mn-N,N complexes under study enable quantitative ATH of acetophenones to the corresponding chiral alcohols with 75-87% ee.
AB - The catalytic asymmetric transfer hydrogenation (ATH) of ketones is a powerful methodology for the practical and efficient installation of chiral centers. Herein, we describe the synthesis, characterization, and catalytic application of a series of manganese complexes bearing simple chiral diamine ligands. We performed an extensive experimental and computational mechanistic study and present the first detailed experimental kinetic study of Mn-catalyzed ATH. We demonstrate that conventional mechanistic approaches toward catalyst optimization fail and how apparently different precatalysts lead to identical intermediates and thus catalytic performance. Ultimately, the Mn-N,N complexes under study enable quantitative ATH of acetophenones to the corresponding chiral alcohols with 75-87% ee.
UR - http://www.scopus.com/inward/record.url?scp=85071689627&partnerID=8YFLogxK
U2 - 10.1021/acs.organomet.9b00457
DO - 10.1021/acs.organomet.9b00457
M3 - Article
AN - SCOPUS:85071689627
VL - 38
SP - 3187
EP - 3196
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 16
ER -