Scope of the Two-step, One-pot Palladium-catalyzed Borylation/Suzuki Cross-coupling Reaction Utilizing Bis-boronic Acid

Overview

Journal J Org Chem

Publisher American Chemical Society

Specialty Chemistry

Date 2012 Sep 22

PMID 22994557

Citations 14

Authors

Gary A Molander

Sarah L J Trice

Steven M Kennedy

Affiliations

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Abstract

The use of bis-boronic acid for the direct synthesis of boronic acids has greatly facilitated the two-step, one-pot borylation/Suzuki cross-coupling reaction between aryl and heteroaryl halides. With use of Buchwald's second-generation XPhos preformed catalyst, high yields of cross-coupled products were obtained for most substrates. The method also allows an efficient two-step, one-pot synthesis, providing access to three distinct cross-coupled products after column chromatography. The method also provides a rapid and convenient route to teraryl compounds.

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References

Join B, Yamamoto T, Itami K . Iridium catalysis for C-H bond arylation of heteroarenes with iodoarenes. Angew Chem Int Ed Engl. 2009; 48(20):3644-7. DOI: 10.1002/anie.200806358. View

Alacid E, Najera C . First cross-coupling reaction of potassium aryltrifluoroborates with organic chlorides in aqueous media catalyzed by an oxime-derived palladacycle. Org Lett. 2008; 10(21):5011-4. DOI: 10.1021/ol802024j. View

Nad S, Roller S, Haag R, Breinbauer R . Electrolysis as an efficient key step in the homogeneous polymer-supported synthesis of N-substituted pyrroles. Org Lett. 2006; 8(3):403-6. DOI: 10.1021/ol052096d. View

Prieto M, Zurita E, Rosa E, Munoz L, Lloyd-Williams P, Giralt E . Arylboronic acids and arylpinacolboronate esters in Suzuki coupling reactions involving indoles. Partner role swapping and heterocycle protection. J Org Chem. 2004; 69(20):6812-20. DOI: 10.1021/jo0491612. View

Han J, Liu Y, Guo R . Facile synthesis of highly stable gold nanoparticles and their unexpected excellent catalytic activity for Suzuki-Miyaura cross-coupling reaction in water. J Am Chem Soc. 2009; 131(6):2060-1. DOI: 10.1021/ja808935n. View

Leermann T, Leroux F, Colobert F . Highly efficient one-pot access to functionalized arylboronic acids via noncryogenic bromine/magnesium exchanges. Org Lett. 2011; 13(17):4479-81. DOI: 10.1021/ol2016252. View

Ishiyama T, Isou H, Kikuchi T, Miyaura N . Ortho-C-H borylation of benzoate esters with bis(pinacolato)diboron catalyzed by iridium-phosphine complexes. Chem Commun (Camb). 2009; 46(1):159-61. DOI: 10.1039/b910298a. View

Baudoin O, Guenard D, Gueritte F . Palladium-catalyzed borylation of ortho-substituted phenyl halides and application to the one-pot synthesis of 2,2'-disubstituted biphenyls. J Org Chem. 2001; 65(26):9268-71. DOI: 10.1021/jo005663d. View

Quasdorf K, Riener M, Petrova K, Garg N . Suzuki-Miyaura coupling of aryl carbamates, carbonates, and sulfamates. J Am Chem Soc. 2009; 131(49):17748-9. PMC: 2801021. DOI: 10.1021/ja906477r. View

10.

Deng H, Jung J, Liu T, Kuntz K, Snapper M, Hoveyda A . Total synthesis of anti-HIV agent chloropeptin I. J Am Chem Soc. 2004; 125(30):9032-4. DOI: 10.1021/ja030249r. View

11.

Molander G, Trice S, Dreher S . Palladium-catalyzed, direct boronic acid synthesis from aryl chlorides: a simplified route to diverse boronate ester derivatives. J Am Chem Soc. 2010; 132(50):17701-3. PMC: 3075417. DOI: 10.1021/ja1089759. View

12.

Jung M, Lazarova T . New Efficient Method for the Total Synthesis of (S,S)-Isodityrosine from Natural Amino Acids. J Org Chem. 2001; 64(9):2976-2977. DOI: 10.1021/jo9902751. View

13.

Yamada Y, Sarkar S, Uozumi Y . Self-assembled poly(imidazole-palladium): highly active, reusable catalyst at parts per million to parts per billion levels. J Am Chem Soc. 2012; 134(6):3190-8. DOI: 10.1021/ja210772v. View

14.

Yang W, He H, Drueckhammer D . Computer-Guided Design in Molecular Recognition: Design and Synthesis of a Glucopyranose Receptor This work was supported by the National Institutes of Health (grant DK5523402). . Angew Chem Int Ed Engl. 2001; 40(9):1714-1718. View

15.

Mor M, Rivara S, Lodola A, Plazzi P, Tarzia G, Duranti A . Cyclohexylcarbamic acid 3'- or 4'-substituted biphenyl-3-yl esters as fatty acid amide hydrolase inhibitors: synthesis, quantitative structure-activity relationships, and molecular modeling studies. J Med Chem. 2004; 47(21):4998-5008. DOI: 10.1021/jm031140x. View

16.

Sau S, Santra S, Sen T, Mandal S, Koley D . Abnormal N-heterocyclic carbene palladium complex: living catalyst for activation of aryl chlorides in Suzuki-Miyaura cross coupling. Chem Commun (Camb). 2011; 48(4):555-7. DOI: 10.1039/c1cc15732a. View

17.

Molander G, Trice S, Kennedy S, Dreher S, Tudge M . Scope of the palladium-catalyzed aryl borylation utilizing bis-boronic acid. J Am Chem Soc. 2012; 134(28):11667-73. PMC: 3407959. DOI: 10.1021/ja303181m. View

18.

Knapp D, Gillis E, Burke M . A general solution for unstable boronic acids: slow-release cross-coupling from air-stable MIDA boronates. J Am Chem Soc. 2009; 131(20):6961-3. PMC: 7309699. DOI: 10.1021/ja901416p. View

19.

Mkhalid I, Barnard J, Marder T, Murphy J, Hartwig J . C-H activation for the construction of C-B bonds. Chem Rev. 2009; 110(2):890-931. DOI: 10.1021/cr900206p. View

20.

Han Z, Pinkner J, Ford B, Obermann R, Nolan W, Wildman S . Structure-based drug design and optimization of mannoside bacterial FimH antagonists. J Med Chem. 2010; 53(12):4779-92. PMC: 2894565. DOI: 10.1021/jm100438s. View