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Review
. 2020 Oct 21;142(42):17859-17875.
doi: 10.1021/jacs.0c09193. Epub 2020 Oct 5.

Structurally Modified Norbornenes: A Key Factor to Modulate Reaction Selectivity in the Palladium/Norbornene Cooperative Catalysis

Renhe Li  1 , Guangbin Dong  1
Affiliations
Review

Structurally Modified Norbornenes: A Key Factor to Modulate Reaction Selectivity in the Palladium/Norbornene Cooperative Catalysis

Renhe Li et al. J Am Chem Soc. .

Abstract

Palladium/norbornene (Pd/NBE) cooperative catalysis has received enormous attention and found numerous synthetic applications in the past two decades. Considering the critical roles that NBE plays in the catalytic cycle, the use of structurally modified NBEs (smNBEs), starting from 2015, has become an important approach to address limitations and modulate reaction selectivity in Pd/NBE catalysis. This Perspective highlights the development of three types of smNBEs: C1-substituted, C2-substituted, and C5-substituted or C5,C6-disubstituted NBEs, as well as their synthetic applications toward site-selective C-H functionalization. A focus is on the structure-activity relationship of smNBEs in these reactions, and rationales for using smNBEs in many cases have also been provided.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1.
Scheme 1.
Pd/NBE Cooperative Catalysis
Scheme 2.
Scheme 2.
Overcoming the ortho constraint with C1-smNBEs
Scheme 3.
Scheme 3.
Scope and Late-stage Functionalization of Bioactive Compounds
Scheme 4.
Scheme 4.
C2-Substituted smNBEs
Scheme 5.
Scheme 5.
Meta Alkylation and Arylation of Substituted Phenylacetamides Using C2-Substituted smNBEs
Scheme 6.
Scheme 6.
Meta Amination, Alkynylation and Chlorination of Aniline and Phenol Derivatives
Scheme 7.
Scheme 7.
Enantioselective Meta C–H Arylation and Alkylation Enabled by a Chiral smNBE
Scheme 8.
Scheme 8.
Direct Meta Arylation of Electron-Rich Arenes, Electron-Deficient Heteroarenes and Fluorobenzenes.
Scheme 9.
Scheme 9.
Remote C–H Arylation of Benzoazines, Tetrahydroisoquinolines and Phenylpropanoic Acids
Scheme 10.
Scheme 10.
Vicinal Difunctionalization of Thiophenes
Scheme 11.
Scheme 11.
Direct Annulation between Aryl Iodides and Epoxides
Scheme 12.
Scheme 12.
Asymmetric Annulation between Aryl Iodides and Epoxides
Scheme 13.
Scheme 13.
Asymmetric ortho arylation of Aryl Iodides
Scheme 14.
Scheme 14.
NBE Effect for the Meta-Substituted Aryl Iodides
Scheme 15.
Scheme 15.
Ortho/Ipso Difunctionalization of Vinyl Triflates/Halides via Pd/NBE Catalysis
Scheme 16.
Scheme 16.
Reported C5-Substituted and C5, C6-Disubstituted NBEs
Scheme 17.
Scheme 17.
Ortho Acylation of Haloarenes Enabled by C5 Methylamide-Substituted NBE
Scheme 18.
Scheme 18.
Pd/NBE-Catalyzed Ortho Alkylation Reaction with Epoxides
Scheme 19.
Scheme 19.
Ortho Alkylation/Ipso Redox-Relay Heck Cascade
Scheme 20.
Scheme 20.
Aziridines as Electrophiles in Catellani-type Reactions
Scheme 21.
Scheme 21.
Ortho Thiolation of Aryl Iodide with Thiosulfonates
Scheme 22.
Scheme 22.
Ortho Methylation of Aryl Halides
Scheme 23.
Scheme 23.
Ortho Glycosylation of Aryl Iodides
Scheme 24.
Scheme 24.
Pd(II)-Initiated Ortho Alkylation and Arylation of Arylboronates
Scheme 25.
Scheme 25.
Pd(II)-Catalyzed Meta Alkylation of Nosyl-Protected Phenylalanines
Scheme 26.
Scheme 26.
Pd(II)-Catalyzed Distal Alkenyl C–H Functionalization
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