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Investigation and comparison of the mechanistic steps in the [(Cp*MCl2)2] (Cp* = C5Me5; M = Rh, Ir)-catalyzed oxidative annulation of isoquinolones with alkynes.
Chemistry. 2013 Jan 02; 19(1):358-64.C

Abstract

The mechanism of the [(Cp*MCl(2))(2)] (M = Rh, Ir)-catalyzed oxidative annulation reaction of isoquinolones with alkynes was investigated in detail. In the first acetate-assisted C-H-activation process (cyclometalated step) and the subsequent mono-alkyne insertion into the M-C bonds of the cyclometalated compounds, both Rh and Ir complexes participated well. However, the desired final products, dibenzo[a,g]quinolizin-8-one derivatives, were only formed in high yield when the Rh species participated in the final oxidative coupling of the C-N bond. Moreover, a Rh(I) sandwich intermediate was isolated during this transformation. The iridium complexes were found to be inactive in the oxidative coupling processes. All of the relevant intermediates were fully characterized and determined by single-crystal X-ray diffraction analysis. Based on this mechanistic study, a Rh(III)→Rh(I)→Rh(III) catalytic cycle was proposed for this reaction.

Authors+Show Affiliations

State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, PR China.No affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article

Language

eng

PubMed ID

23168678

Citation

Wang, Nuancheng, et al. "Investigation and Comparison of the Mechanistic Steps in the [(Cp*MCl2)2] (Cp* = C5Me5; M = Rh, Ir)-catalyzed Oxidative Annulation of Isoquinolones With Alkynes." Chemistry (Weinheim an Der Bergstrasse, Germany), vol. 19, no. 1, 2013, pp. 358-64.
Wang N, Li B, Song H, et al. Investigation and comparison of the mechanistic steps in the [(Cp*MCl2)2] (Cp* = C5Me5; M = Rh, Ir)-catalyzed oxidative annulation of isoquinolones with alkynes. Chemistry. 2013;19(1):358-64.
Wang, N., Li, B., Song, H., Xu, S., & Wang, B. (2013). Investigation and comparison of the mechanistic steps in the [(Cp*MCl2)2] (Cp* = C5Me5; M = Rh, Ir)-catalyzed oxidative annulation of isoquinolones with alkynes. Chemistry (Weinheim an Der Bergstrasse, Germany), 19(1), 358-64. https://doi.org/10.1002/chem.201203374
Wang N, et al. Investigation and Comparison of the Mechanistic Steps in the [(Cp*MCl2)2] (Cp* = C5Me5; M = Rh, Ir)-catalyzed Oxidative Annulation of Isoquinolones With Alkynes. Chemistry. 2013 Jan 2;19(1):358-64. PubMed PMID: 23168678.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Investigation and comparison of the mechanistic steps in the [(Cp*MCl2)2] (Cp* = C5Me5; M = Rh, Ir)-catalyzed oxidative annulation of isoquinolones with alkynes. AU - Wang,Nuancheng, AU - Li,Bin, AU - Song,Haibin, AU - Xu,Shansheng, AU - Wang,Baiquan, Y1 - 2012/11/21/ PY - 2012/09/20/received PY - 2012/11/22/entrez PY - 2012/11/22/pubmed PY - 2012/11/22/medline SP - 358 EP - 64 JF - Chemistry (Weinheim an der Bergstrasse, Germany) JO - Chemistry VL - 19 IS - 1 N2 - The mechanism of the [(Cp*MCl(2))(2)] (M = Rh, Ir)-catalyzed oxidative annulation reaction of isoquinolones with alkynes was investigated in detail. In the first acetate-assisted C-H-activation process (cyclometalated step) and the subsequent mono-alkyne insertion into the M-C bonds of the cyclometalated compounds, both Rh and Ir complexes participated well. However, the desired final products, dibenzo[a,g]quinolizin-8-one derivatives, were only formed in high yield when the Rh species participated in the final oxidative coupling of the C-N bond. Moreover, a Rh(I) sandwich intermediate was isolated during this transformation. The iridium complexes were found to be inactive in the oxidative coupling processes. All of the relevant intermediates were fully characterized and determined by single-crystal X-ray diffraction analysis. Based on this mechanistic study, a Rh(III)→Rh(I)→Rh(III) catalytic cycle was proposed for this reaction. SN - 1521-3765 UR - https://www.unboundmedicine.com/medline/citation/23168678/Investigation_and_comparison_of_the_mechanistic_steps_in_the_[_Cp_MCl2_2]__Cp__=_C5Me5 L2 - https://doi.org/10.1002/chem.201203374 DB - PRIME DP - Unbound Medicine ER -
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