Amino alcohols as ligands for nickel-catalyzed Suzuki reactions of unactivated alkyl halides, including secondary alkyl chlorides, with arylboronic acids

Journal of the American Chemical Society

Volumn 128, Issue 16, 2006, Pages 5360-5361

  González Bobes, Francisco ^a   Fu, Gregory C ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AMINOALCOHOL; BORONIC ACID DERIVATIVE; CHLORIDE; CYCLOHEXANOL DERIVATIVE; HALIDE; NICKEL;

ADDITION REACTION; ARTICLE; CATALYSIS; CATALYST; CYCLIZATION; DIASTEREOISOMER; SUZUKI REACTION;

AMINO ALCOHOLS; BORONIC ACIDS; CATALYSIS; HALOGENS; LIGANDS; NICKEL;

EID: 33646447380     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0613761     Document Type: Article

References (24)

1. (a) Metal-Catalyzed Cross-Coupling Reactions: de Meijere, A., Diederich, F., Eds.; Wiley-VCH: New York, 2004.
2. (b) Handbook of Organopalladium Chemistry for Organic Synthesis; Negishi, E.-i., Ed.; Wiley-Interscience: New York, 2002.
3. For pioneering studies, see: (a) Ishiyama, T.; Abe, S.; Miyaura, N.; Suzuki, A. Chem. Lett. 1992, 691-694.
4. (b) Devasagayaraj, A.; Stüdemann, T.; Knochel, P. Angew. Chem., Int. Ed. Engl. 1995, 34, 2723-2725.
5. For recent reviews, see: (a) Frisch, A. C.; Beller, M. Angew. Chem., Int. Ed. 2005, 44, 674-688.
6. (b) Netherton, M. R.; Fu, G. C. Topics in Organometallic Chemistry: Palladium in Organic Synthesis; Tsuji, J., Ed.; Springer: New York, 2005.
7. Netherton, M. R.; Fu, G. C. Adv. Synth. Catal. 2004, 346, 1525-1532.
8. Zhou, J.; Fu, G. C. J. Am. Chem. Soc. 2004, 126, 1340-1341.
9. For asymmetric Negishi reactions of alkyl halides, see: (a) Fischer, C.; Fu, G. C. J. Am. Chem. Soc. 2005, 127, 4594-4595.
10. (b) Arp, F. O.; Fu, G. C. J. Am. Chem. Soc. 2005, 127, 10482-10483.
11. For a review of chiral bipyridine and phenanthroline ligands, see: Chelucci, G.; Thummel, R. P. Chem. Rev. 2002, 102, 3129-3170.
12. Notes: (a) The hydrochloride salt of trans-2-aminocyclohexanol was employed since that is the form in which it is commonly supplied.
13. (b) In a 10 mmol experiment, the coupling depicted in entry 6 of Table 1 proceeds in 85% yield (1.6 g of product).
14. (c) For cross-couplings of electron-rich arylboronic acids, 2 equiv of the boronic acid was used, due to competitive protodeborylation.
15. (d) The coupling of cyclohexyl bromide with phenylboronic acid can be achieved under microwave conditions under air (57% yield according to GC analysis versus a calibrated internal standard; 80 °C, 250 W, 5 min; not extensively optimized).
16. (e) Reactions of several heteroaryl-, vinyl-, and alkylboronic acids proceeded in relatively poor yield (<30%). We have not yet examined the capacity of other nickel/ amino alcohol catalysts to achieve Suzuki cross-couplings of these families of substrates.
17. For the Suzuki reaction illustrated in entry 2 of Table 1, the Ni/ bathophenanthroline catalyst (eq 1) furnishes <5% of the cross-coupling product.
18. For the cross-coupling depicted in entry 5 of Table 1, we have not detected the formation of any product resulting from reaction of the secondary alkyl chloride.
19. (a) Pandey, G.; Rao, K. S. S. P.; Palit, D. K.; Mittal, J. P. J. Org. Chem. 1998, 63, 3968-3978.
20. (b) Hackmann, C.; Schäfer, H. J. Tetrahedron 1993, 49, 4559-4574.
21. (c) Mayer, S.; Prandi, J.; Bamhaoud, T.; Bakkas, S.; Guillou, O. Tetrahedron 1998, 54, 8753-8770.
22. For an earlier discussion, see: Powell, D. A.; Maki, T.; Fu, G. C. J. Am. Chem. Soc. 2005, 127, 510-511. Under our standard conditions, alkyl tosylates are essentially unreactive (< 10% yield), presumably due to their reluctance to undergo oxidative addition via a radical pathway.
23. Notes: (a) Future studies will be directed at gaining an understanding of the interplay among various reaction parameters and their impact on the efficiency of these cross-coupling processes.
24. (b) This method is not effective for ortho-substituted arylboronic acids (<30% yield).