This report investigates the fundamental basis for rather surprising patterns of reactivity in Brønsted acid-mediated cyclizations of pyrrole substrates bearing pendant Michael acceptors that were identified during syntheses of Stemona alkaloids. Integrated experimental and theoretical studies reveal the profound influence that substituent effects have on the viability of these transformations. Additionally, we identify that electronic effects, in addition to barrier-lowering secondary orbital interactions within transition states, account for the exclusive preference for 7-endo-trig cyclizations over 6-exo-trig cyclizations.

Item Type:	Refereed Article
Keywords:	stemona alkaloids, pyrrole, Michael addition, DFT
Research Division:	Chemical Sciences
Research Group:	Organic chemistry
Research Field:	Organic chemical synthesis
Objective Division:	Expanding Knowledge
Objective Group:	Expanding knowledge
Objective Field:	Expanding knowledge in the chemical sciences
UTAS Author:	Olivier, WJ (Mr Wesley Olivier)
UTAS Author:	Babaahmadi, R (Mr Rasool Babaahmadi)
UTAS Author:	Ariafard, A (Associate Professor Alireza Ariafard)
UTAS Author:	Bissember, AC (Associate Professor Alex Bissember)
UTAS Author:	Smith, JA (Associate Professor Jason Smith)
ID Code:	147736
Year Published:	2021
Funding Support:	Australian Research Council (FT200100049)
Web of Science® Times Cited:	2
Deposited By:	Chemistry
Deposited On:	2021-11-12
Last Modified:	2022-04-07
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