Nickel-catalyzed Carbon-carbon Bond-forming Reactions of Unactivated Tertiary Alkyl Halides: Suzuki Arylations

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2013 Jan 4

PMID 23281960

Citations 62

Authors

Susan L Zultanski

Gregory C Fu

Affiliations

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Abstract

The first Suzuki cross-couplings of unactivated tertiary alkyl electrophiles are described. The method employs a readily accessible catalyst (NiBr(2)·diglyme/4,4'-di-tert-butyl-2,2'-bipyridine, both commercially available) and represents the initial example of the use of a group 10 catalyst to cross-couple unactivated tertiary electrophiles to form C-C bonds. This approach to the synthesis of all-carbon quaternary carbon centers does not suffer from isomerization of the alkyl group, in contrast with the umpolung strategy for this bond construction (cross-coupling of a tertiary alkylmetal with an aryl electrophile). Preliminary mechanistic studies are consistent with the generation of a radical intermediate along the reaction pathway.

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References

King S, Reid C, Forbes K, Hanks G . A systematic review of oxycodone in the management of cancer pain. Palliat Med. 2011; 25(5):454-70. DOI: 10.1177/0269216311401948. View

Zhou J, Fu G . Suzuki cross-couplings of unactivated secondary alkyl bromides and iodides. J Am Chem Soc. 2004; 126(5):1340-1. DOI: 10.1021/ja039889k. View

Jones G, Martin J, McFarland C, Allen O, Hall R, Haley A . Ligand redox effects in the synthesis, electronic structure, and reactivity of an alkyl-alkyl cross-coupling catalyst. J Am Chem Soc. 2006; 128(40):13175-83. DOI: 10.1021/ja063334i. View

Someya H, Ohmiya H, Yorimitsu H, Oshima K . Silver-catalyzed benzylation and allylation reactions of tertiary and secondary alkyl halides with grignard reagents. Org Lett. 2008; 10(5):969-71. DOI: 10.1021/ol800038a. View

Glasspoole B, Crudden C . Cross-coupling: The final frontier. Nat Chem. 2011; 3(12):912-3. DOI: 10.1038/nchem.1210. View

Wilsily A, Tramutola F, Owston N, Fu G . New directing groups for metal-catalyzed asymmetric carbon-carbon bond-forming processes: stereoconvergent alkyl-alkyl Suzuki cross-couplings of unactivated electrophiles. J Am Chem Soc. 2012; 134(13):5794-7. PMC: 3333791. DOI: 10.1021/ja301612y. View

Sai M, Someya H, Yorimitsu H, Oshima K . Copper-catalyzed reaction of alkyl halides with cyclopentadienylmagnesium reagent. Org Lett. 2008; 10(12):2545-7. DOI: 10.1021/ol800814k. View

Terao J, Kambe N . Cross-coupling reaction of alkyl halides with grignard reagents catalyzed by Ni, Pd, or Cu complexes with pi-carbon ligand(s). Acc Chem Res. 2008; 41(11):1545-54. DOI: 10.1021/ar800138a. View

Lamoureux G, Artavia G . Use of the adamantane structure in medicinal chemistry. Curr Med Chem. 2010; 17(26):2967-78. DOI: 10.2174/092986710792065027. View

10.

Dudnik A, Fu G . Nickel-catalyzed coupling reactions of alkyl electrophiles, including unactivated tertiary halides, to generate carbon-boron bonds. J Am Chem Soc. 2012; 134(25):10693-7. PMC: 3384763. DOI: 10.1021/ja304068t. View

11.

Ohmiya H, Tsuji T, Yorimitsu H, Oshima K . Cobalt-catalyzed cross-coupling reactions of alkyl halides with allylic and benzylic Grignard reagents and their application to tandem radical cyclization/cross-coupling reactions. Chemistry. 2004; 10(22):5640-8. DOI: 10.1002/chem.200400545. View

12.

Hu X . Cross coupling of non-activated alkyl halides by a nickel pincer complex. Chimia (Aarau). 2010; 64(4):231-4. DOI: 10.2533/chimia.2010.231. View

13.

Phapale V, Bunuel E, Garcia-Iglesias M, Cardenas D . Ni-catalyzed cascade formation of C(sp3)--C(sp3) bonds by cyclization and cross-coupling reactions of iodoalkanes with alkyl zinc halides. Angew Chem Int Ed Engl. 2007; 46(46):8790-5. DOI: 10.1002/anie.200702528. View

14.

Suzuki A . Cross-coupling reactions of organoboranes: an easy way to construct C-C bonds (Nobel Lecture). Angew Chem Int Ed Engl. 2011; 50(30):6722-37. DOI: 10.1002/anie.201101379. View

15.

Lin X, Lee Phillips D . Density functional theory studies of negishi alkyl-alkyl cross-coupling reactions catalyzed by a methylterpyridyl-Ni(I) complex. J Org Chem. 2008; 73(10):3680-8. DOI: 10.1021/jo702497p. View

16.

Glorius F . Asymmetric cross-coupling of non-activated secondary alkyl halides. Angew Chem Int Ed Engl. 2008; 47(44):8347-9. DOI: 10.1002/anie.200803509. View

17.

Mitamura Y, Asada Y, Murakami K, Someya H, Yorimitsu H, Oshima K . Silver-catalyzed benzylation and allylation of tertiary alkyl bromides with organozinc reagents. Chem Asian J. 2010; 5(6):1487-93. DOI: 10.1002/asia.201000068. View

18.

Gonzalez-Bobes F, Fu G . Amino alcohols as ligands for nickel-catalyzed suzuki reactions of unactivated alkyl halides, including secondary alkyl chlorides, with arylboronic acids. J Am Chem Soc. 2006; 128(16):5360-1. DOI: 10.1021/ja0613761. View

19.

Joshi-Pangu A, Wang C, Biscoe M . Nickel-catalyzed Kumada cross-coupling reactions of tertiary alkylmagnesium halides and aryl bromides/triflates. J Am Chem Soc. 2011; 133(22):8478-81. PMC: 8036247. DOI: 10.1021/ja202769t. View

20.

Tsuji T, Yorimitsu H, Oshima K . Cobalt-catalyzed coupling reaction of alkyl halides with allylic grignard reagents. Angew Chem Int Ed Engl. 2002; 41(21):4137-9. DOI: 10.1002/1521-3773(20021104)41:21<4137::AID-ANIE4137>3.0.CO;2-0. View