Unusual C–H Bond Activation and C(sp3)–C(sp3) Bond Formation at an Fe(II) Bis(amide) Carbene Complex

Autor:	Guang Wu, Kevin Guevara, Anthony T. Wong, Gabriel Ménard
Rok vydání:	2019
Předmět:	Methanesulfonyl chloride Organic Chemistry Bond formation Medicinal chemistry Chloride Inorganic Chemistry IMes chemistry.chemical_compound chemistry Amide medicine Physical and Theoretical Chemistry Chemoselectivity Bimetallic strip Carbene medicine.drug
Zdroj:	Organometallics. 39:116-122
ISSN:	1520-6041 0276-7333
DOI:	10.1021/acs.organomet.9b00674
Popis:	Treatment of (IMes)Fe(NTMS2)2 with 4 equiv of methanesulfonyl chloride (MsCl = MeSO2Cl) resulted in a complex reaction sequence involving substitution of two TMS groups for Ms, followed by the unexpected C(sp3)–H bond activation of Ms and subsequent C(sp3)–C(sp3) bond formation to generate the bimetallic Fe complex, [IMesH]2[Cl2Fe(N(TMS)SO2(CH2)2SO2N(TMS))2FeCl2] (1) (IMes = 1,3-bis(2,4,6-trimethylphenyl)-imidazole-2-ylidene; TMS = SiMe3). Extending this C–H activation/C–C bond-forming chemistry to larger alkylsulfonyl chloride chains (i.e., Et and Bu) similarly resulted in C–C coupling, but with decreased chemoselectivity. Detailed mechanistic studies, including using possible intermediate model compounds, were performed in order to elucidate a unifying mechanism for this previously unknown avenue to C(sp3)–C(sp3) bond formation.
Databáze:	OpenAIRE
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