Enantioenriched Allylesters Via a Copper-Catalyzed Diene Carboesterification with Alkyltrifluoroborates and Carboxylic Acids

Overview

Journal J Org Chem

Publisher American Chemical Society

Specialty Chemistry

Date 2024 Jan 9

PMID 38194284

Authors

Jonathan J Kennedy-Ellis

Alexis D Kelleher

Jaffer A Sayeed

Ameya S Burde

Sherry R Chemler

Affiliations

Soon will be listed here.

Abstract

The rapid synthesis of a range of enantioenriched allylic esters is enabled by a new 3-component catalytic enantioselective 1,2-carboesterification of readily available dienes with carboxylic acids and potassium alkyltrifluoroborates. The chiral copper catalyst, formed in situ from Cu(OTf) and (4,4')-2,2'-(cyclopentane-1,1-diyl)bis(4-phenyl-4,5-dihydrooxazole), is implicated in both the generation of alkyl radicals from the alkyltrifluoroborates as well as the enantioselective formation of C-O bonds. Potassium salts of primary and secondary alkyltrifluoroborates as well as several benzylic trifluoroborates, -butyltrifluoroborate, and phenyltrifluoroborate participate in the reaction. The regioselectivity and enantioselectivity are strongly impacted by variations in all of the reaction components, which in turn are thought to impact the C-O bond-forming reductive elimination from a [Cu(III)] intermediate.

References

Crespi S, Fagnoni M . Generation of Alkyl Radicals: From the Tyranny of Tin to the Photon Democracy. Chem Rev. 2020; 120(17):9790-9833. PMC: 8009483. DOI: 10.1021/acs.chemrev.0c00278. View

Wang Z, Wang Y, Rao Z, Liu C, Pan X, Guo L . General Method for Selective Three-Component Carboacylation of Alkenes via Visible-Light Dual Photoredox/Nickel Catalysis. Org Lett. 2023; 25(10):1673-1677. DOI: 10.1021/acs.orglett.3c00307. View

Andrus M, Zhou Z . Highly enantioselective copper-bisoxazoline-catalyzed allylic oxidation of cyclic olefins with tert-butyl p-nitroperbenzoate. J Am Chem Soc. 2002; 124(30):8806-7. DOI: 10.1021/ja026266i. View

Wang P, Wu X, Cheng Y, Jiang M, Xiao W, Chen J . Photoinduced Copper-Catalyzed Asymmetric Three-Component Coupling of 1,3-Dienes: An Alternative to Kharasch-Sosnovsky Reaction. Angew Chem Int Ed Engl. 2021; 60(42):22956-22962. DOI: 10.1002/anie.202110084. View

Zhu X, Jian W, Huang M, Li D, Li Y, Zhang X . Asymmetric radical carboesterification of dienes. Nat Commun. 2021; 12(1):6670. PMC: 8602303. DOI: 10.1038/s41467-021-26843-2. View

Li Z, Fang G, Gu Q, Liu X . Recent advances in copper-catalysed radical-involved asymmetric 1,2-difunctionalization of alkenes. Chem Soc Rev. 2019; 49(1):32-48. DOI: 10.1039/c9cs00681h. View

Ge L, Li Y, Jian W, Bao H . Alkyl Esterification of Vinylarenes Enabled by Visible-Light-Induced Decarboxylation. Chemistry. 2017; 23(49):11767-11770. DOI: 10.1002/chem.201702385. View

Um C, Chemler S . Synthesis of 2-Aryl- and 2-Vinylpyrrolidines via Copper-Catalyzed Coupling of Styrenes and Dienes with Potassium β-Aminoethyl Trifluoroborates. Org Lett. 2016; 18(10):2515-8. PMC: 4874882. DOI: 10.1021/acs.orglett.6b01259. View

Chen J, Liang Y, Wang P, Li G, Zhang B, Qian H . Photoinduced Copper-Catalyzed Asymmetric C-O Cross-Coupling. J Am Chem Soc. 2021; 143(33):13382-13392. DOI: 10.1021/jacs.1c06535. View

10.

Hemric B, Chen A, Wang Q . Copper-Catalyzed 1,2-Amino Oxygenation of 1,3-Dienes: A Chemo-, Regio-, and Site-Selective Three-Component Reaction with -Acylhydroxylamines and Carboxylic Acids. ACS Catal. 2019; 9(11):10070-10076. PMC: 6830571. DOI: 10.1021/acscatal.9b03076. View

11.

Kennedy-Ellis J, Boldt E, Chemler S . Synthesis of Benzylureas and Related Amine Derivatives via Copper-Catalyzed Three-Component Carboamination of Styrenes. Org Lett. 2020; 22(21):8365-8369. PMC: 8170827. DOI: 10.1021/acs.orglett.0c02988. View

12.

Maji B, Yamamoto H . Catalytic Enantioselective Nitroso Diels-Alder Reaction. J Am Chem Soc. 2015; 137(50):15957-63. DOI: 10.1021/jacs.5b11273. View

13.

Boyd D, Sharma N, Sbircea L, Murphy D, Belhocine T, Malone J . Azaarene cis-dihydrodiol-derived 2,2'-bipyridine ligands for asymmetric allylic oxidation and cyclopropanation. Chem Commun (Camb). 2008; (43):5535-7. DOI: 10.1039/b814678k. View

14.

Lei G, Zhang H, Chen B, Xu M, Zhang G . Copper-catalyzed enantioselective arylalkynylation of alkenes. Chem Sci. 2020; 11(6):1623-1628. PMC: 7069229. DOI: 10.1039/c9sc04029c. View

15.

Molander G, Sandrock D . Potassium trifluoroborate salts as convenient, stable reagents for difficult alkyl transfers. Curr Opin Drug Discov Devel. 2009; 12(6):811-23. PMC: 2908178. View

16.

Mayoral J, Rodriguez-Rodriguez S, Salvatella L . Theoretical insights into enantioselective catalysis: the mechanism of the Kharasch-Sosnovsky reaction. Chemistry. 2008; 14(30):9274-85. DOI: 10.1002/chem.200800638. View

17.

Reymond S, Cossy J . Copper-catalyzed Diels-Alder reactions. Chem Rev. 2008; 108(12):5359-406. DOI: 10.1021/cr078346g. View

18.

Shono T, Harada T . Catalytic enantioselective synthesis of secondary allylic alcohols from terminal alkynes and aldehydes via 1-alkenylboron reagents. Org Lett. 2010; 12(22):5270-3. DOI: 10.1021/ol1023213. View

19.

Zhu R, Buchwald S . Versatile Enantioselective Synthesis of Functionalized Lactones via Copper-Catalyzed Radical Oxyfunctionalization of Alkenes. J Am Chem Soc. 2015; 137(25):8069-77. PMC: 4490856. DOI: 10.1021/jacs.5b04821. View

20.

Shikora J, Um C, Khoder Z, Chemler S . Saturated oxygen and nitrogen heterocycles oxidative coupling of alkyltrifluoroborates with alkenols, alkenoic acids and protected alkenylamines. Chem Sci. 2020; 10(40):9265-9269. PMC: 7003886. DOI: 10.1039/c9sc02835h. View