Control of Stereoselectivity in Diverse Hapalindole Metabolites is Mediated by Cofactor‐Induced Combinatorial Pairing of Stig Cyclases. Issue 21 (19th March 2020)

• Record Type: Journal Article
• Authors: Li, Shasha; Newmister, Sean A.; Lowell, Andrew N.; Zi, Jiachen; Chappell, Callie R.; Yu, Fengan; Hohlman, Robert M.; Orjala, Jimmy; Williams, Robert M.; Sherman, David H.
• Is Part Of: Angewandte Chemie international edition. Volume 59:Issue 21(2020)
• Page Start: 8166
• Page End: 8172
• Publication Date: 2020-03-19
• Subjects: biocatalysis -- cyclases -- indoles -- oligomerization -- rearrangements; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201913686
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Stereospecific polycyclic core formation of hapalindoles and fischerindoles is controlled by Stig cyclases through a three‐step cascade involving Cope rearrangement, 6‐ exo ‐trig cyclization, and a final electrophilic aromatic substitution. Reported here is a comprehensive study of all currently annotated Stig cyclases, revealing that these proteins can assemble into heteromeric complexes, induced by Ca 2+, to cooperatively control the stereochemistry of hapalindole natural products. Abstract : Assembly control : Stereospecific formation of the polycyclic core of hapalindoles and fischerindoles is controlled by Stig cyclases through a three‐step cascade involving Cope rearrangement, 6‐ exo ‐trig cyclization, and a final electrophilic aromatic substitution. The proteins can assemble into heteromeric complexes, induced by Ca 2+, to cooperatively control the stereochemistry of hapalindole natural products.