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

Hongming Jin (), Wen-Yan Tong, Jing Zhang, Matthias Rudolph, Frank Rominger, Xu Shen, Shuanglin Qu () and A. Stephen K. Hashmi ()
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Hongming Jin: Nanjing University of Chinese Medicine
Wen-Yan Tong: Hunan University
Jing Zhang: Nanjing University of Chinese Medicine
Matthias Rudolph: Universität Heidelberg
Frank Rominger: Universität Heidelberg
Xu Shen: Nanjing University of Chinese Medicine
Shuanglin Qu: Hunan University
A. Stephen K. Hashmi: Universität Heidelberg

Nature Communications, 2022, vol. 13, issue 1, 1-11

Abstract: Abstract Pt(II) and Au(III)-mediated intermolecular divergent annulations of benzofurazans and ynamides highlighted the N- to O-selectivity of tunable metal carbene intermediates. PtCl2 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-PyrAuCl3) 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.

Date: 2022
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DOI: 10.1038/s41467-022-29326-0

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