Enantioselective Catalysis Coupled with Stereodivergent Cyclization Strategies Enables Rapid Syntheses of (+)-Limaspermidine and (+)-Kopsihainanine A

Pritchett, Beau P. and Donckele, Etienne J. and Stoltz, Brian M. (2017) Enantioselective Catalysis Coupled with Stereodivergent Cyclization Strategies Enables Rapid Syntheses of (+)-Limaspermidine and (+)-Kopsihainanine A. Angewandte Chemie International Edition, 56 (41). pp. 12624-12627. ISSN 1433-7851. PMCID PMC5896324. doi:10.1002/anie.201707304. https://resolver.caltech.edu/CaltechAUTHORS:20170905-134054944

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Abstract

Enantioselective Pd-catalyzed allylic alkylations of dihydropyrido[1,2-a]indolone (DHPI) substrates were used to construct the C20-quaternary stereocenters of multiple monoterpene indole alkaloids. Stereodivergent Pictet–Spengler and Bischler–Napieralski cyclization/reduction cascades furnish the cis- and trans-fused azadecalin subunits present in Aspidosperma and Kopsia alkaloids, respectively, en route to highly efficient syntheses of (+)-limaspermidine and (+)-kopsihainanine A.

Item Type:

Article

Related URLs:

URL	URL Type	Description
https://doi.org/10.1002/anie.201707304	DOI	Article
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5896324	PubMed Central	Article

ORCID:

Author	ORCID
Pritchett, Beau P.	0000-0001-9922-9160
Donckele, Etienne J.	0000-0001-9112-1753
Stoltz, Brian M.	0000-0001-9837-1528

Additional Information:

© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Issue online: 27 September 2017; Version of record online: 5 September 2017; Manuscript Received: 18 July 2017. The authors wish to thank NIH-NIGMS (R01GM080269), Amgen, the Gordon and Betty Moore Foundation, the Caltech Center for Catalysis and Chemical Synthesis, and Caltech for financial support. B.P.P. thanks the NSF for a predoctoral fellowship (Grant DGE-1144469). E.J.D. thanks the Swiss National Science Foundation (SNSF) for a postdoctoral fellowship (Grant P2EZP2_168798). The authors thank Dr. Mona Shahgholi and Naseem Torian (Caltech) for mass spectrometry assistance, Dr. Scott Virgil (Caltech) for instrumentation assistance, and Larry Henling (Caltech) for X-ray crystallographic assistance. The authors declare no conflict of interest.

Funders:

Funding Agency	Grant Number
NIH	R01GM080269
Amgen	UNSPECIFIED
Gordon and Betty Moore Foundation	UNSPECIFIED
Caltech	UNSPECIFIED
NSF Graduate Research Fellowship	DGE-1144469
Swiss National Science Foundation (SNSF)	P2EZP2_168798

Subject Keywords:

allylic alkylation; asymmetric catalysis; monoterpene indole alkaloids; stereodivergent cyclizations; total synthesis

Issue or Number:

PubMed Central ID:

PMC5896324

DOI:

10.1002/anie.201707304

Record Number:

CaltechAUTHORS:20170905-134054944

Persistent URL:

https://resolver.caltech.edu/CaltechAUTHORS:20170905-134054944

Official Citation:

B. P. Pritchett, E. J. Donckele, B. M. Stoltz, Angew. Chem. Int. Ed. 2017, 56, 12624.

Usage Policy:

No commercial reproduction, distribution, display or performance rights in this work are provided.

ID Code:

81144

Collection:

CaltechAUTHORS

Deposited By:

Tony Diaz

Deposited On:

05 Sep 2017 20:46

Last Modified:

22 Mar 2022 19:34

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