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Ir-Catalyzed Asymmetric Allylic Alkylation of Dialkyl Malo-nates Enabling the Construction of Enantioenriched All-Carbon Quaternary Centers

Moghadam, Farbod A. and Hicks, Elliot F. and Sercel, Zachary P. and Cusumano, Alexander Q. and Bartberger, Michael D. and Stoltz, Brian M. (2022) Ir-Catalyzed Asymmetric Allylic Alkylation of Dialkyl Malo-nates Enabling the Construction of Enantioenriched All-Carbon Quaternary Centers. . (Unpublished) https://resolver.caltech.edu/CaltechAUTHORS:20220322-742009000

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Abstract

An enantioselective iridium-catalyzed allylic alkylation of malonates with trisubstituted allylic electrophiles to form all-carbon quaternary stereocenters is reported. This cross-coupling reaction features unprecedented reactivity at ambient temperature, particularly for challenging fully alkyl-substituted allylic electrophiles, and enables the preparation of a wide range of enantio-enriched products in up to 93% yield and 97% ee. The products of this transformation can be readily converted to a number of valuable building blocks including vicinal quaternary stereodiads and β-quaternary acids. This method was also used to prepare an enantioenriched intermediate facilitating the asymmetric formal synthesis of the sporochnol family of natural products.


Item Type:Report or Paper (Discussion Paper)
Related URLs:
URLURL TypeDescription
https://doi.org/10.26434/chemrxiv-2022-n4bswDOIDiscussion Paper
ORCID:
AuthorORCID
Cusumano, Alexander Q.0000-0002-2914-2008
Bartberger, Michael D.0000-0002-5167-3139
Stoltz, Brian M.0000-0001-9837-1528
Additional Information:The content is available under CC BY NC 4.0 License. The authors would like to thank Dr. Mona Shagholi for mass spectrometry assistance and Dr. Scott Virgil for assistance with instrumentation. The NIH-NIGMS (R01GM080269) and Caltech are thanked for their support of our research program. E. F. H. and Z. P. S. would like to thank the NSF GRFP for funding. Author Contributions. The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. The authors declare no conflict of interest
Funders:
Funding AgencyGrant Number
NIHR01GM080269
CaltechUNSPECIFIED
NSF Graduate Research FellowshipUNSPECIFIED
Subject Keywords:quaternary centers; iridium catalysis; enantioselectivity; acyclic stereocontrol
DOI:10.26434/chemrxiv-2022-n4bsw
Record Number:CaltechAUTHORS:20220322-742009000
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20220322-742009000
Official Citation:Moghadam F, Hicks E, Sercel Z, Cusumano A, Bartberger M, Stoltz B. Ir-Catalyzed Asymmetric Allylic Alkylation of Dialkyl Malo-nates Enabling the Construction of Enantioenriched All-Carbon Quaternary Centers . ChemRxiv. 2022. doi:10.26434/chemrxiv-2022-n4bsw
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:113993
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:23 Mar 2022 17:29
Last Modified:23 Mar 2022 17:29

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