Palladium-Catalyzed Carbonylative Difunctionalization of Unactivated Alkenes Initiated by Unstabilized Enolates

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2023 Jun 15

PMID 37319375

Authors

Pengpeng Zhang

Timothy R Newhouse

Affiliations

Soon will be listed here.

Abstract

This report describes the first example of palladium-catalyzed carbonylative difunctionalization of unactivated alkenes initiated by enolate nucleophiles. The approach involves initiation by an unstabilized enolate nucleophile under an atmospheric pressure of CO and termination with a carbon electrophile. This process is compatible with a diverse range of electrophiles, including aryl, heteroaryl, and vinyl iodides to yield synthetically useful 1,5-diketone products, which were demonstrated to be precursors for multi-substituted pyridines. A Pd -dimer complex with two bridging CO units was observed although its role in catalysis is not yet understood.

References

Li J, Li M, Bruhn T, Katele F, Xiao Q, Pedpradab P . Thaixylomolins A-C: limonoids featuring two new motifs from the Thai Xylocarpus moluccensis. Org Lett. 2013; 15(14):3682-5. DOI: 10.1021/ol401556m. View

Huang D, Olivieri D, Sun Y, Zhang P, Newhouse T . Nickel-Catalyzed Difunctionalization of Unactivated Alkenes Initiated by Unstabilized Enolates. J Am Chem Soc. 2019; 141(41):16249-16254. DOI: 10.1021/jacs.9b09245. View

Derosa J, Apolinar O, Kang T, Tran V, Engle K . Recent developments in nickel-catalyzed intermolecular dicarbofunctionalization of alkenes. Chem Sci. 2021; 11(17):4287-4296. PMC: 8152638. DOI: 10.1039/c9sc06006e. View

Zhang P, Wang J, Robertson Z, Newhouse T . Coordination-Controlled Nickel-Catalyzed Benzylic Allylation of Unactivated Electron-Deficient Heterocycles. Angew Chem Int Ed Engl. 2022; 61(22):e202200602. DOI: 10.1002/anie.202200602. View

Zhang P, Huang D, Newhouse T . Aryl-Nickel-Catalyzed Benzylic Dehydrogenation of Electron-Deficient Heteroarenes. J Am Chem Soc. 2019; 142(4):1757-1762. DOI: 10.1021/jacs.9b12706. View

Johansson Seechurn C, Sperger T, Scrase T, Schoenebeck F, Colacot T . Understanding the Unusual Reduction Mechanism of Pd(II) to Pd(I): Uncovering Hidden Species and Implications in Catalytic Cross-Coupling Reactions. J Am Chem Soc. 2017; 139(14):5194-5200. DOI: 10.1021/jacs.7b01110. View

Hazari N, Melvin P, Beromi M . Well-defined nickel and palladium precatalysts for cross-coupling. Nat Rev Chem. 2017; 1. PMC: 5637737. DOI: 10.1038/s41570-017-0025. View

Bai Y, Davis D, Dai M . Natural Product Synthesis via Palladium-Catalyzed Carbonylation. J Org Chem. 2017; 82(5):2319-2328. DOI: 10.1021/acs.joc.7b00009. View

Chen M, Wang X, Yang P, Kou X, Ren Z, Guan Z . Palladium-Catalyzed Enantioselective Heck Carbonylation with a Monodentate Phosphoramidite Ligand: Asymmetric Synthesis of (+)-Physostigmine, (+)-Physovenine, and (+)-Folicanthine. Angew Chem Int Ed Engl. 2020; 59(29):12199-12205. DOI: 10.1002/anie.202003288. View

10.

Holman K, Stanko A, Reisman S . Palladium-catalyzed cascade cyclizations involving C-C and C-X bond formation: strategic applications in natural product synthesis. Chem Soc Rev. 2021; 50(14):7891-7908. DOI: 10.1039/d0cs01385d. View

11.

Carmona R, Koster O, Roque Duarte Correia C . Chiral N,N Ligands Enabling Palladium-Catalyzed Enantioselective Intramolecular Heck-Matsuda Carbonylation Reactions by Sequential Migratory and CO Insertions. Angew Chem Int Ed Engl. 2018; 57(37):12067-12070. DOI: 10.1002/anie.201805831. View

12.

Ma K, Martin B, Yin X, Dai M . Natural product syntheses via carbonylative cyclizations. Nat Prod Rep. 2018; 36(1):174-219. DOI: 10.1039/c8np00033f. View

13.

Xu J, Wang L, Wu X . Non-Noble Metal-Catalyzed Carbonylative Multi-Component Reactions. Chem Asian J. 2022; 17(22):e202200928. DOI: 10.1002/asia.202200928. View

14.

Wu F, Yuan Y, Schunemann C, Kamer P, Wu X . Copper-Catalyzed Regioselective Borocarbonylative Coupling of Unactivated Alkenes with Alkyl Halides: Synthesis of β-Boryl Ketones. Angew Chem Int Ed Engl. 2020; 59(26):10451-10455. DOI: 10.1002/anie.202002714. View

15.

Buscemi G, Miller P, Kealey S, Gee A, Long N, Passchier J . Rapid carbonylative coupling reactions using palladium(I) dimers: applications to 11CO-radiolabelling for the synthesis of PET tracers. Org Biomol Chem. 2011; 9(9):3499-503. DOI: 10.1039/c1ob05268c. View

16.

Wickham L, Giri R . Transition Metal (Ni, Cu, Pd)-Catalyzed Alkene Dicarbofunctionalization Reactions. Acc Chem Res. 2021; 54(17):3415-3437. PMC: 8860250. DOI: 10.1021/acs.accounts.1c00329. View

17.

Denes F, Perez-Luna A, Chemla F . Addition of metal enolate derivatives to unactivated carbon-carbon multiple bonds. Chem Rev. 2010; 110(4):2366-447. DOI: 10.1021/cr800420x. View

18.

Barder T . Synthesis, structural, and electron topographical analyses of a dialkylbiaryl phosphine/arene-ligated palladium(I) dimer: enhanced reactivity in Suzuki-Miyaura coupling reactions. J Am Chem Soc. 2006; 128(3):898-904. DOI: 10.1021/ja0558995. View

19.

Wang J, Strom A, Hartwig J . Mechanistic Studies of Palladium-Catalyzed Aminocarbonylation of Aryl Chlorides with Carbon Monoxide and Ammonia. J Am Chem Soc. 2018; 140(25):7979-7993. PMC: 9135163. DOI: 10.1021/jacs.8b04073. View

20.

Mamone P, Grunberg M, Fromm A, Khan B, Goossen L . [Pd(μ-Br)(P(t)Bu3)]2 as a highly active isomerization catalyst: synthesis of enol esters from allylic esters. Org Lett. 2012; 14(14):3716-9. DOI: 10.1021/ol301563g. View