Palladium/norbornene-catalyzed Distal Alkenyl C-H Arylation and Alkylation of Cis-olefins

Overview

Journal Tetrahedron

Specialty Chemistry

Date 2021 Oct 25

PMID 34690377

Citations 1

Authors

Zhao Wu

Nina Fatuzzo

Guangbin Dong

Affiliations

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Abstract

In this full article, a detailed study of a distal alkenyl C-H arylation and alkylation through the palladium/norbornene (NBE) cooperative catalysis is described. Both aminopyridine- and oxime ether-type directing groups have been found effective for this transformation, allowing functionalization of diverse allyl amines and homoallyl alcohols. In addition, the C5,C6-substititued NBEs show optimal reactivity and selectivity. Various cis-olefins can be transformed to the corresponding arylated or alkylated trisubstituted alkenes with excellent regio- and stereoselectivity. Preliminary mechanistic studies support the Catellani pathway instead of the Heck pathway.

Citing Articles

Rapid Access to Multisubstituted Acrylamides from Cyclic Ketones via Palladium/Norbornene Cooperative Catalysis.

Wu Z, Dong G Angew Chem Int Ed Engl. 2022; 61(17):e202201239.

PMID: 35199445 PMC: 9007888. DOI: 10.1002/anie.202201239.

References

Wu Z, Fatuzzo N, Dong G . Distal Alkenyl C-H Functionalization via the Palladium/Norbornene Cooperative Catalysis. J Am Chem Soc. 2020; 142(6):2715-2720. PMC: 7075342. DOI: 10.1021/jacs.9b11479. View

Wang J, Dong Z, Yang C, Dong G . Modular and regioselective synthesis of all-carbon tetrasubstituted olefins enabled by an alkenyl Catellani reaction. Nat Chem. 2019; 11(12):1106-1112. PMC: 7098644. DOI: 10.1038/s41557-019-0358-y. View

Chen S, Liu Z, Yang T, Hua Y, Zhou Z, Cheng H . The Discovery of a Palladium(II)-Initiated Borono-Catellani Reaction. Angew Chem Int Ed Engl. 2018; 57(24):7161-7165. DOI: 10.1002/anie.201803865. View

Wang H, Beiring B, Yu D, Collins K, Glorius F . [3]Dendralene synthesis: rhodium(III)-catalyzed alkenyl C-H activation and coupling reaction with allenyl carbinol carbonate. Angew Chem Int Ed Engl. 2013; 52(47):12430-4. DOI: 10.1002/anie.201306754. View

Schreib B, Carreira E . Palladium-Catalyzed Regioselective C-H Iodination of Unactivated Alkenes. J Am Chem Soc. 2019; 141(22):8758-8763. DOI: 10.1021/jacs.9b03998. View

Lyons T, Sanford M . Palladium-catalyzed ligand-directed C-H functionalization reactions. Chem Rev. 2010; 110(2):1147-69. PMC: 2836499. DOI: 10.1021/cr900184e. View

Wang X, Gong W, Fang L, Zhu R, Li S, Engle K . Ligand-enabled meta-C-H activation using a transient mediator. Nature. 2015; 519(7543):334-8. PMC: 4368492. DOI: 10.1038/nature14214. View

Meng K, Li T, Yu C, Shen C, Zhang J, Zhong G . Geminal group-directed olefinic C-H functionalization via four- to eight-membered exo-metallocycles. Nat Commun. 2019; 10(1):5109. PMC: 6841671. DOI: 10.1038/s41467-019-13098-1. View

Motti E, Ca N, Deledda S, Fava E, Panciroli F, Catellani M . Palladium-catalyzed unsymmetrical aryl couplings in sequence leading to o-teraryls: dramatic olefin effect on selectivity. Chem Commun (Camb). 2010; 46(24):4291-3. DOI: 10.1039/c000526f. View

10.

Wang J, Dong G . Palladium/Norbornene Cooperative Catalysis. Chem Rev. 2019; 119(12):7478-7528. PMC: 7075350. DOI: 10.1021/acs.chemrev.9b00079. View

11.

Meng G, Lam N, Lucas E, Saint-Denis T, Verma P, Chekshin N . Achieving Site-Selectivity for C-H Activation Processes Based on Distance and Geometry: A Carpenter's Approach. J Am Chem Soc. 2020; 142(24):10571-10591. PMC: 7485751. DOI: 10.1021/jacs.0c04074. View

12.

Liu M, Yang P, Karunananda M, Wang Y, Liu P, Engle K . C(alkenyl)-H Activation via Six-Membered Palladacycles: Catalytic 1,3-Diene Synthesis. J Am Chem Soc. 2018; 140(17):5805-5813. PMC: 6089246. DOI: 10.1021/jacs.8b02124. View

13.

Ye J, Lautens M . Palladium-catalysed norbornene-mediated C-H functionalization of arenes. Nat Chem. 2015; 7(11):863-70. DOI: 10.1038/nchem.2372. View

14.

Monks B, Fruchey E, Cook S . Iron-catalyzed C(sp²)-H alkylation of carboxamides with primary electrophiles. Angew Chem Int Ed Engl. 2014; 53(41):11065-9. DOI: 10.1002/anie.201406594. View

15.

White J, Carter R, Sundermann K, Wartmann M . Total synthesis of epothilone B, epothilone D, and cis- and trans-9,10-dehydroepothilone D. J Am Chem Soc. 2001; 123(23):5407-13. DOI: 10.1021/ja010454b. View

16.

Tsai A, Bergman R, Ellman J . Asymmetric synthesis of (-)-incarvillateine employing an intramolecular alkylation via Rh-catalyzed olefinic C-H bond activation. J Am Chem Soc. 2008; 130(20):6316-7. PMC: 2713182. DOI: 10.1021/ja8012159. View

17.

He J, Wasa M, Chan K, Shao Q, Yu J . Palladium-Catalyzed Transformations of Alkyl C-H Bonds. Chem Rev. 2017; 117(13):8754-8786. PMC: 5516964. DOI: 10.1021/acs.chemrev.6b00622. View

18.

Xu Y, Dong G . sp C-H activation -type directing groups. Chem Sci. 2018; 9(6):1424-1432. PMC: 5892337. DOI: 10.1039/c7sc04768a. View

19.

Sambiagio C, Schonbauer D, Blieck R, Dao-Huy T, Pototschnig G, Schaaf P . A comprehensive overview of directing groups applied in metal-catalysed C-H functionalisation chemistry. Chem Soc Rev. 2018; 47(17):6603-6743. PMC: 6113863. DOI: 10.1039/c8cs00201k. View

20.

Martins A, Candito D, Lautens M . Palladium-catalyzed reductive ortho-arylation: evidence for the decomposition of 1,2-dimethoxyethane and subsequent arylpalladium(II) reduction. Org Lett. 2010; 12(22):5186-8. DOI: 10.1021/ol1019037. View