a
Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
b
Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, Suita, Osaka 565-0871, Japan
a
Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
b
Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, Suita, Osaka 565-0871, Japan
› Author AffiliationsThis work was supported by JST CREST Grant Number JPMJCR20R3, Japan. It was also supported by JSPS KAKENHI grant numbers JP18K19079, JP18H01977, and JP19K05455. F.W. acknowledges support from China Scholarship Council (CSC) under the Grant CSC number 201906420088.
Homologation of alkyl acetates, alkyl ethers, acetals, and ketals was accomplished via formal insertion of diazo esters into carbon–carbon σ-bonds. The combined Lewis acid InI3 with Me3SiBr catalyzed the homologation of alkyl acetates and alkyl ethers. That of acetals and ketals was catalyzed solely by the use of InBr3. The key point of the homologation mechanism is that the indium-based Lewis acids have the appropriate amount of Lewis acidity to achieve both the abstraction and release of leaving groups. The abstraction of a leaving group by an indium-based Lewis acid and the electrophilic addition of carbocation or oxonium intermediates to diazo esters followed by the rearrangement of carbon substituents provide the corresponding cation intermediates. Finally, the leaving group that is captured by the Lewis acid bonds with cation intermediates to furnish the homologated products.
6 Cheng reported rhodium-catalyzed formal insertion of O–C(sp3)–C(sp2) into C–C σ-bonds of 1,3-dicarbonyl compounds using diazo esters and DMF:
Ba D,
Wen S,
Tian Q,
Chen Y,
Lv W,
Cheng G.
Nat. Commun. 2020; 11: 4219
12 CCDC 2075523 (3aa) contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures
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