VIP Event Grushin

On the beautiful sunny day of September 13, 2016, abcr GmbH, Karlsruhe, was pleased to welcome a group of its customers and collaborators from both industry and academia for a special event, an invited seminar by Dr. Vladimir Grushin of K&G Technologies LLC, WY, USA.  In his talk 'Direct Cupration of Fluoroform: From Waste to High-Value Trifluoromethylated Compounds', Vladimir Grushin shared his results on the development of novel methods to efficiently trifluoromethylate a variety of substrates in the most economical way.

Following active exchange of ideas and discussions during the reception and after the seminar, the participants enjoyed a tour of the abcr facilities given by Dr. Jan Schuricht, abcr Managing Director. The tour included a visit to the storage rooms and detailed explanations of safety measurements taken while handling customers' orders.

The attendees and the abcr team unanimously concurred in the opinion that the event was highly successful, featuring many useful discussions of cooperation between the groups in the future.

Direct Cupration of Fluoroform
Speaker – Vladimir Grushin

Direct Cupration of Fluoroform:
From Waste to High-Value Trifluoromethylated Compounds

Vladimir V. Grushin
K&G Technologies LLC, WY, USA

Trifluoromethylated building blocks and intermediates are in increasingly high demand for the synthesis of agrochemicals, pharmaceuticals, and specialty materials.¹ Readily available fluoroform (CHF₃), a side-product of the fluoropolymer and fluorochemicals industries and a potent greenhouse gas, is by far the best CF₃ source for trifluoromethylation reactions.^1,2However, chemoselective activation of highly inert fluoroform is exceedingly challenging. In recent years, a novel promising methodology has emerged for CHF₃ activation with transition metals. This presentation will focus on our contributions to the area (Scheme below), including (i) the first reactions of direct cupration^1-5 and palladation⁶ of fluoroform to furnish CuCF₃ and PdCF₃ complexes in nearly quantitative yield; (ii) the development of new, lowcost, highly efficient, and selective fluoroalkylation methods with our CuRf (R_f = CF₃, C₂F₅) reagents prepared from CHF₃ and C₂F₅H;^7-14 and (iii) remarkable mechanisms of the cupration of CHF₃⁵ and aromatic trifluoromethylation reactions with CuCF₃.^15,16

Keywords: Fluoroform · Trifluoromethylation · Pentafluoroethylation · Reaction Mechanisms

¹Tomashenko, O. A.; Grushin, V. V. Chem. Rev. 2011, 111, 4475. ²Grushin, V. V. Chim. Oggi 2014, 32, 81. ³Zanardi, A; Novikov, M. A.; Martin, E.; Benet-Buchholz, J.; Grushin, V. V. J. Am. Chem. Soc. 2011, 133, 20901. ⁴Mazloomi, Z.; Bansode, A.; Benavente, P.; Lishchynskyi, A.; Urakawa, A.; Grushin, V. V. Org. Process Res. Dev. 2014, 18, 1020. ⁵Konovalov, A. I.; Benet-Buchholz, J.; Martin, E.; Grushin, V. V. Angew. Chem. Int. Ed. 2013, 52, 11637. ⁶Takemoto, S.; Grushin, V. V. J. Am. Chem. Soc. 2013, 135, 16837. ⁷Novák, P.; Lishchynskyi, A.; Grushin, V. V. Angew. Chem. Int. Ed. 2012, 51, 7767. ⁸Novák, P.; Lishchynskyi, A.; Grushin, V. V. J. Am. Chem. Soc. 2012, 134, 16167. ⁹Lishchynskyi, A.; Novikov, M. A.; Martin, E.; Escudero-Adán, E. C.; Novák, P.; Grushin, V. V. J. Org. Chem. 2013, 78, 11126. ¹⁰Lishchynskyi, A.; Grushin, V. V. J. Am. Chem. Soc.2013, 135, 12584. ¹¹Lishchynskyi, A.; Berthon, G.; Grushin, V. V. Chem. Commun. 2014, 50, 10237. ¹²Lishchynskyi, A.; Mazloomi, Z.; Grushin, V. V. Synlett 2015, 26, 45. ¹³Romine, A. M.; Nebra, N.; Konovalov, A. I.; Martin, E.; Benet-Buchholz, J.; Grushin, V. V. Angew. Chem., Int. Ed. 2015, 54, 2745. ¹⁴Panferova, L. I.; Miloserdov, F. M.; Lishchynskyi, A.; Martínez Belmonte, M.; Benet-Buchholz, J.; Grushin, V. V. Angew. Chem., Int. Ed. 2015, 54, 5218. ¹⁵Konovalov, A. I.; Lishchynskyi, A.; Grushin, V. V. J. Am. Chem. Soc. 2014, 136, 13410. ¹⁶Nebra, N.; Grushin, V. V. J. Am. Chem. Soc. 2014, 136, 16998.