Indole-ynones as Privileged Substrates for Radical Dearomatizing Spirocyclization Cascades

TY - JOUR

T1 - Indole-ynones as Privileged Substrates for Radical Dearomatizing Spirocyclization Cascades

AU - Inprung, Nantachai

AU - Ho, Hon Eong

AU - Rossi-Ashton, James A

AU - Epton, Ryan G

AU - Whitwood, Adrian C

AU - Lynam, Jason M

AU - Taylor, Richard J K

AU - James, Michael J

AU - Unsworth, William P

N1 - © 2022 American Chemical Society. 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 - 2022/1/21

Y1 - 2022/1/21

N2 - Indole-ynones have been established as general substrates for radical dearomatizing spirocyclization cascade reactions. Five distinct and varied synthetic protocols have been developed─cyanomethylation, sulfonylation, trifluoromethylation, stannylation and borylation─using a variety of radical generation modes, ranging from photoredox catalysis to traditional AIBN methods. The simple and easily prepared indole-ynones can be used to rapidly generate diverse, densely functionalized spirocycles and have the potential to become routinely used to explore radical reactivity. Experimental and computational investigations support the proposed radical cascade mechanism and suggest that other new methods are now primed for development.

AB - Indole-ynones have been established as general substrates for radical dearomatizing spirocyclization cascade reactions. Five distinct and varied synthetic protocols have been developed─cyanomethylation, sulfonylation, trifluoromethylation, stannylation and borylation─using a variety of radical generation modes, ranging from photoredox catalysis to traditional AIBN methods. The simple and easily prepared indole-ynones can be used to rapidly generate diverse, densely functionalized spirocycles and have the potential to become routinely used to explore radical reactivity. Experimental and computational investigations support the proposed radical cascade mechanism and suggest that other new methods are now primed for development.

U2 - 10.1021/acs.orglett.1c04098

DO - 10.1021/acs.orglett.1c04098

M3 - Article

C2 - 34985297

SN - 1523-7060

VL - 24

SP - 668

EP - 674

JO - Organic letters

JF - Organic letters

IS - 2

ER -