Internal nucleophilic catalyst mediated cyclisation/ring expansion cascades for the synthesis of medium-sized lactones and lactams

TY - JOUR

T1 - Internal nucleophilic catalyst mediated cyclisation/ring expansion cascades for the synthesis of medium-sized lactones and lactams

AU - Lawer, Aggie

AU - Rossi-Ashton, James A

AU - Stephens, Thomas C

AU - Challis, Bradley J

AU - Epton, Ryan G

AU - Lynam, Jason M

AU - Unsworth, William Paul

N1 - © 2019 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details.

PY - 2019/9/24

Y1 - 2019/9/24

N2 - A strategy for the synthesis of medium-sized lactones and lactams from linear precursors is described in which an amine acts as an internal nucleophilic catalyst to facilitate a novel cyclisation/ring expansion cascade sequence. This method obviates the need to use high-dilution conditions usually associated with medium-ring cyclisation protocols, as the reactions operate exclusively via kinetically favourable 'normal' sized cyclic transition states. This same feature also enables biaryl-containing medium-sized rings to be prepared with complete atroposelectivity via point-to-axial chirality transfer.

AB - A strategy for the synthesis of medium-sized lactones and lactams from linear precursors is described in which an amine acts as an internal nucleophilic catalyst to facilitate a novel cyclisation/ring expansion cascade sequence. This method obviates the need to use high-dilution conditions usually associated with medium-ring cyclisation protocols, as the reactions operate exclusively via kinetically favourable 'normal' sized cyclic transition states. This same feature also enables biaryl-containing medium-sized rings to be prepared with complete atroposelectivity via point-to-axial chirality transfer.

KW - atropisomers

KW - axial chirality

KW - medium-sized rings

KW - pyridines

KW - ring expansion

UR - http://www.scopus.com/inward/record.url?scp=85071160568&partnerID=8YFLogxK

U2 - 10.1002/anie.201907206

DO - 10.1002/anie.201907206

M3 - Article

C2 - 31340086

SN - 1433-7851

VL - 58

SP - 13942

EP - 13947

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

IS - 39

ER -