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Rhodium-catalyzed anti-Markovnikov hydroamination of vinylarenes.
J Am Chem Soc. 2003 May 14; 125(19):5608-9.JA

Abstract

The transition metal-catalyzed anti-Markovnikov hydroamination of unactivated vinylarenes with a rhodium complex of DPEphos is reported. The reaction of electron-neutral or electron-rich vinylarenes with a variety of secondary amines in the presence of catalyst forms the products from anti-Markovnikov hydroamination in high yields. Reactions of morpholine, N-phenylpiperazine, N-Boc-piperazine, piperidine, 2,5-dimethylmorpholine, and perhydroisoquinoline reacted with styrene to form the amine product in 51-71% yield. Reactions of a variety of vinylarenes with morpholine generated amine as the major product. Reactions of morpholine with electron-poor vinylarenes gave lower amine:enamine ratios than reactions of electron-rich vinylarenes at the same concentration of vinylarene, but conditions were developed with lower concentrations of electron-poor vinylarene to maintain formation of the amine as the major product. Reactions of dimethylamine with vinylarenes were fast and formed amine as the major product. Mechanistic studies on the hydroamination process showed that the amine:enamine ratio was lower for reactions conducted with higher concentrations of vinylarene and that one vinylarene influences the selectivity for reaction of another. A mechanism proceeding through a metallacyclic intermediate that opens in the presence of a second vinylarene accounts for these and other mechanistic observations.

Authors+Show Affiliations

Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, USA.No affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, P.H.S.

Language

eng

PubMed ID

12733880

Citation

Utsunomiya, Masaru, et al. "Rhodium-catalyzed anti-Markovnikov Hydroamination of Vinylarenes." Journal of the American Chemical Society, vol. 125, no. 19, 2003, pp. 5608-9.
Utsunomiya M, Kuwano R, Kawatsura M, et al. Rhodium-catalyzed anti-Markovnikov hydroamination of vinylarenes. J Am Chem Soc. 2003;125(19):5608-9.
Utsunomiya, M., Kuwano, R., Kawatsura, M., & Hartwig, J. F. (2003). Rhodium-catalyzed anti-Markovnikov hydroamination of vinylarenes. Journal of the American Chemical Society, 125(19), 5608-9.
Utsunomiya M, et al. Rhodium-catalyzed anti-Markovnikov Hydroamination of Vinylarenes. J Am Chem Soc. 2003 May 14;125(19):5608-9. PubMed PMID: 12733880.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Rhodium-catalyzed anti-Markovnikov hydroamination of vinylarenes. AU - Utsunomiya,Masaru, AU - Kuwano,Ryoichi, AU - Kawatsura,Motoi, AU - Hartwig,John F, PY - 2003/5/8/pubmed PY - 2003/7/3/medline PY - 2003/5/8/entrez SP - 5608 EP - 9 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 125 IS - 19 N2 - The transition metal-catalyzed anti-Markovnikov hydroamination of unactivated vinylarenes with a rhodium complex of DPEphos is reported. The reaction of electron-neutral or electron-rich vinylarenes with a variety of secondary amines in the presence of catalyst forms the products from anti-Markovnikov hydroamination in high yields. Reactions of morpholine, N-phenylpiperazine, N-Boc-piperazine, piperidine, 2,5-dimethylmorpholine, and perhydroisoquinoline reacted with styrene to form the amine product in 51-71% yield. Reactions of a variety of vinylarenes with morpholine generated amine as the major product. Reactions of morpholine with electron-poor vinylarenes gave lower amine:enamine ratios than reactions of electron-rich vinylarenes at the same concentration of vinylarene, but conditions were developed with lower concentrations of electron-poor vinylarene to maintain formation of the amine as the major product. Reactions of dimethylamine with vinylarenes were fast and formed amine as the major product. Mechanistic studies on the hydroamination process showed that the amine:enamine ratio was lower for reactions conducted with higher concentrations of vinylarene and that one vinylarene influences the selectivity for reaction of another. A mechanism proceeding through a metallacyclic intermediate that opens in the presence of a second vinylarene accounts for these and other mechanistic observations. SN - 0002-7863 UR - https://www.unboundmedicine.com/medline/citation/12733880/Rhodium_catalyzed_anti_Markovnikov_hydroamination_of_vinylarenes_ L2 - https://doi.org/10.1021/ja0293608 DB - PRIME DP - Unbound Medicine ER -