Platinum-Catalyzed Substitution of Allylic Fluorides

Abstract

Allyl fluorides are reactive toward Pt-catalyzed alkylation with malonate and likewise toward N-and Onucleophiles under mild conditions. The reactivity of fluoride as a leaving group equals or exceeds that of the esters and carbonates commonly employed in allylic alkylation. The order of leaving-group ability with Pt catalysts was found to be F ≥ OCO 2 Me ≫ OBz ≥ OAc. This discouraged the application of platinum catalysts for the reverse reaction, fluorination of allylic substrates. Fluoride displacement involves predominant or complete retention of configuration in all the observed cases, and this was confirmed as a general feature of Pt catalysis, the stereochemical integrity being as high or higher as in Pd catalysis for the examples chosen.

Synthesis of monofluoroalkenes using a Pt-catalyzed amination reaction of cyclic 3,3-difluoropropenes with secondary aliphatic amines

“…Disappointingly, using the similar conditions as reported by Gouverneur [6], no conversion was observed (entry 1). However, performing the reaction at 70 8C instead gave a moderate yield of the desired monofluoroalkene 2 (entry 2).…”

“…Recently, Gouverneur and coworkers [6] reported the use of Ptcatalyzed allylic amination of allylic fluorides ( Fig. 2A).…”

DFT Studies on Ni-Mediated C–F Cleavage for the Synthesis of Cyclopentadiene Derivatives

“…Outstanding progress has been made recently in transition-metal-mediated C–F activation reactions and in the development of new catalytic processes for the functionalization of fluoroorganics (Murphy et al, 1997 ; Jones, 2003 ; Mazurek and Schwarz, 2003 ; Ahrens et al, 2015 ). Research on transition metal-catalyzed C ( sp 2 )–F bond activation has been intensively studied (Amii and Uneyama, 2009 ; Braun et al, 2009 ; Laot et al, 2010 ; Ohashi et al, 2011 ; Lv et al, 2012 ; Fujita et al, 2016 ) while C( sp 3 )–F bond activation needs much more exploration (Choi et al, 2011 ; Benedetto et al, 2012 ; Blessley et al, 2012 ; Kuehnel et al, 2012 ; Zhang et al, 2015 ; Huang and Hayashi, 2016 ). Recently, Prof. Ichikawa's group (Ichitsuka et al, 2014 ) developed an efficient synthesis of 2-fluoro-1,3-cyclopentadienes through 2-trifluoromethyl-1-alkenes with alkynes by sequential β-fluorine elimination of a trifluoromethyl group (Equation 1).…”

Efficient and Direct Synthesis of γ‐Amino‐α,β‐Unsaturated Amides by Catalyzed Allylic Substitution of α‐Fluoroenamides: Toward to Synthesis of Hybrid Peptides and Indolizidines

“…The chemistry of allylic fluorides has been extensively studied and recent studies have focused on the palladium catalysis of these allylic fluorides . One example reports the use of a platinum catalyst in an allylic substitution reaction with an amine of a non‐functionalized allyl fluoride . Recently, we have developed a rapid process for access to functionalized α‐fluoroenamides from γ‐silylenamides .…”