BioChem - DOS

Biocatalytic Dynamic Kinetic Resolution for the Synthesis of Atropisomeric Biaryl N-Oxide Lewis Base Catalysts

Angewandte Chemie. international edition

Staniland, Samantha; Adams, Ralph W.; McDouall, Joseph J. W.; Maffucci, Irene; Contini, Alessandro; Grainger, Damian M.; Turner, Nicholas J.; Clayden, Jonathan

<P><B>Abstract</B></P><P>Atropisomeric biaryl pyridine and isoquinoline N&#8208;oxides were synthesized enantioselectively by dynamic kinetic resolution (DKR) of rapidly racemizing precursors exhibiting free bond rotation. The DKR was achieved by ketoreductase (KRED) catalyzed reduction of an aldehyde to form a configurationally stable atropisomeric alcohol, with the substantial increase in rotational barrier arising from the loss of a bonding interaction between the N&#8208;oxide and the aldehyde. Use of different KREDs allowed either the M or P enantiomer to be synthesized in excellent enantiopurity. The enantioenriched biaryl N&#8208;oxide compounds catalyze the asymmetric allylation of benzaldehyde derivatives with allyltrichlorosilane.</P>

2016

1433-7851

1521-3773

55

36

pp.10755-10759

10.1002/anie.201605486

http://click.ndsl.kr/servlet/OpenAPIDetailView?keyValue=05787966&target=NART&cn=NART76222964

https://research-information.bris.ac.uk/files/92910752/Samba_revision_8_7_16.pdf

atropisomerism; biaryls; enzymes; kinetic resolution; organocatalysis