Selective N Functionalization of Methane and Ethane to Aminated Derivatives by Main-Group-Directed C–H Activation

• Published in: Organometallics Vol. 38; no. 11; pp. 2319 - 2322
• Main Authors: Gunsalus, Niles Jensen, Park, Sae Hume, Hashiguchi, Brian G, Koppaka, Anjaneyulu, Smith, Stacey J, Ess, Daniel H, Periana, Roy A
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 10-06-2019
• Subjects: Chemistry
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/acs.organomet.9b00246

To our knowledge, there is no precedent for the direct conversion of light alkanes to aminated products by CH activation. Previous molecular systems reported for alkane amination operate by radical or nitrene-type reactions which generally result in unintended overfunctionalization. Here we disclose the first examples of direct conversion of methane and ethane to aminated products by C–H activation facilitated by electrophilic, main-group complexes dissolved in N-acids. Alkane conversion products were achieved with selectivities up to >95% and yields up to 65% based on added main-group electrophile. Experimental studies and DFT calculations support a C–H activation mechanism to generate a metal–alkyl intermediate that undergoes N-functionalization.