Dichotomy of platinum(II) and gold(III) carbene intermediates switching from N- to O-selectivity

Pt(II) and Au(III)-mediated intermolecular divergent annulations of benzofurazans and ynamides highlighted the N - to O -selectivity of tunable metal carbene intermediates. PtCl 2 with a bulky phosphite ligand resulted in the specific synthesis of six-membered quinoxaline N -oxides and successfully...

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Published in:Nature communications 2022-03, Vol.13 (1), p.1672-1672, Article 1672
Main Authors: Jin, Hongming, Tong, Wen-Yan, Zhang, Jing, Rudolph, Matthias, Rominger, Frank, Shen, Xu, Qu, Shuanglin, Hashmi, A. Stephen K.
Format: Article
Language:English
Subjects:
119/118
140/131
140/58
639/638/403/934
639/638/77/888
Benzimidazoles
Carbenes
Catalysts
Computer applications
Cyclization
Deoxygenation
Divergence
Functional groups
Gold
Humanities and Social Sciences
Intermediates
Mathematical analysis
Methane - analogs & derivatives
multidisciplinary
N-Oxides
Oxides
Platinum
Quinoxaline
Quinoxalines
Science
Science (multidisciplinary)
Selectivity
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Summary:Pt(II) and Au(III)-mediated intermolecular divergent annulations of benzofurazans and ynamides highlighted the N - to O -selectivity of tunable metal carbene intermediates. PtCl 2 with a bulky phosphite ligand resulted in the specific synthesis of six-membered quinoxaline N -oxides and successfully suppressed the in-situ deoxygenation of N -oxides. On the other hand, an unique gold(III) catalyst (2,6-di-MeO-PyrAuCl 3 ) led to the five-membered ring products, benzimidazoles. A broad scope of functional groups was well compatible, delivering better yields and selectivities in contrast to conventional gold(I) catalysts. The different behavior of presumed platinum(II) and gold(III) carbenes with respect to chemoselectivity was intensively examined by experiments and DFT calculations. A detailed mechanistic study, based on DFT calculations, revealed that the highly electrophilic carbocation-like gold(III) carbene triggers an oxophilic cyclization, followed by a cascade ring contraction and acyl migration. On the contrary, the Pt carbene species is less cationic, favoring the formation of the six-membered ring via N -attack. Benzofurazan, a cyclic heterocycle, can form open-chain metal carbene species in the presence of suitable catalysts. Here the authors show divergent reactivity when using gold(III) and platinum(II) catalysts, and perform computational and experimental mechanistic studies to explain the differing reactivity
ISSN:2041-1723
2041-1723
DOI:10.1038/s41467-022-29326-0