Synthesis 2017; 49(06): 1182-1189
DOI: 10.1055/s-0036-1588648
short review
© Georg Thieme Verlag Stuttgart · New York

Role of Fluoride Ions in Palladium-Catalyzed Cross-Coupling Reactions­

Laurence Grimaud
Ecole Normale Supérieure-PSL Research University, Département de Chimie, Sorbonne Universités - UPMC Univ Paris 06, CNRS UMR 8640 PASTEUR, 24 Rue Lhomond, 75231 Paris Cedex 5, France   Email: [email protected]
,
Anny Jutand*
Ecole Normale Supérieure-PSL Research University, Département de Chimie, Sorbonne Universités - UPMC Univ Paris 06, CNRS UMR 8640 PASTEUR, 24 Rue Lhomond, 75231 Paris Cedex 5, France   Email: [email protected]
› Author Affiliations
Further Information

Publication History

Received: 08 October 2016

Accepted: 13 October 2016

Publication Date:
15 November 2016 (online)


Abstract

Fluoride ions are known to promote Suzuki–Miyaura, Hiyama, and Stille reactions [cross-coupling between aryl halides ArX and nucleo­philes Ar′B(OH)2, Ar′Si(OMe)3, and Ar′SnBu3, respectively], where they exert a similar triple role: (1) They favor transmetalation by formation of trans-ArPdFL2 (L = PPh3) complexes that react with the nucleophiles in contrast to trans-ArPdXL2. (2) They catalyze the reductive elimination from trans-ArPdAr′L2 generated in the transmetalation. (3) The final role is negative, by formation of unreactive anionic species [Ar′BF(OH)2], [Ar′SiF(OMe)3], or [Ar′SnFBu3], respectively. Consequently the rate of the rate-determining transmetalation is controlled by the concentration ratio [F]/[nucleophile] which must be less or close to one to ensure fast transmetalation.

1 Introduction

2 Reaction of Fluoride Ions with ArPdXL2 Complexes

3 The Triple Role of Fluoride Ions in Suzuki–Miyaura Reactions

4 The Triple Role of Fluoride Ions in Hiyama Reactions

5 The Triple Role of Fluoride Ions in Stille Reactions

6 Conclusion

 
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