Version 2 2021-06-03, 19:13Version 2 2021-06-03, 19:13
Version 1 2021-03-24, 19:40Version 1 2021-03-24, 19:40
journal contribution
posted on 2021-06-03, 19:13authored byWanjun Chen, Yaping Cheng, Tao Zhang, Yu Mu, Wenqi Jia, Guodu Liu
An efficient nickel-catalyzed stereoselective asymmetric intramolecular
reductive coupling of N-1,6-alkynones is reported.
A P-chiral monophosphine ligand AntPhos was found to be a privileged
catalyst for constructing versatile functionalized chiral pyrrolidine
rings using triethylsilane as the reducing reagent. Concise synthesis
of pyrrolidines with chiral tertiary allylic alcohols was achieved
in high yields (99%), excellent stereoselectivity (>99:1 E/Z), and enantioselectivity (>99:1 er) with very
broad substrate scope. Totally, thirty-five N-1,6-alkynones
were synthesized and applied in this reaction successfully. This reaction
can be scaled up to gram scale without loss of its enantioselectivity.
Ligand effects and reaction mechanism are investigated in detail.
While the developed asymmetric synthesis of pyrrolidine with chiral
tertiary allylic alcohols is anticipated to find wider applications
in organic synthesis and chemical biology, the discovered new reactions
of N-1,6-alkynone with AntPhos using different catalyst
systems would further expanded its new research fields and attract
more detailed explorations in the future.