Introduction
New Template —— Among the various strategies to access alkenyl fluorides, transition metal-mediated fluorination has recently received much attention [1, 2]. However, developing reactions with complementary geometry and regioselectivity of double bond continues to challenge contemporary methodology. This chapter will cover the recent advances in the Pd-, Cu-, and Ag-mediated fluorination for preparing alkenyl fluorides.
Pd-Mediated Fluorination for Preparing Alkenyl Fluorides
An interesting example is the palladium-catalyzed tandem fluorination and cyclization of enynes using N-fluorobenzenesulfonimide (NSFI) as a fluorinating reagent described by Liu and coworkers (Scheme 1) [3]. A variety of enynes reacted with NSFI in the presence of catalytic amounts of Pd(O2CCF3)2, leading to the desired fluorinated 3-benzylidenyllactame with (E)-isomer as the major product. However, the electronic property had a dramatic influence on the reaction yield, with the lower yield obtained...
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References
Landelle G, Bergeron M, Turcotte-Savard M-O, Paquin J-F. 2011. Synthetic approaches to monofluoroalkenes. Chem. Soc. Rev. 40:2867-908
Hollingworth C, Gouverneur V. 2012. Transition metal catalysis and nucleophilic fluorination. Chem. Commun. 48:2929-42
Peng H, Liu G. 2011. Palladium-Catalyzed Tandem Fluorination and Cyclization of Enynes. Org. Lett. 13:772-5
Ye Y, Takada T, Buchwald SL. 2016. Palladium-Catalyzed Fluorination of Cyclic Vinyl Triflates: Effect of TESCF3 as an Additive. Angew. Chem. Int. Ed. 55:15559-63
Heitz W, Knebelkamp A. 1991. Synthesis of fluorostyrenes via palladium-catalyzed reactions of aromatic halides with fluoroolefins. Die Makromolekulare Chemie, Rapid Communications 12:69-75
Matthews DP, Waid PP, Sabol JS, McCarthy JR. 1994. The synthesis of (1-fluorovinyl)tributyltin: A synthetic equivalent for the 1-fluoroethene anion. Tetrahedron Lett. 35:5177-80
Hanamoto T, Kobayashi T, Kondo M. 2001. Fluoride Ion-Assisted Cross-Coupling Reactions of (α-Fluorovinyl)diphenylmethylsilane with Aryl Iodides Catalyzed by Pd(0)/Cu(I) Systems. Synlett 2001:0281-3
Hanamoto T, Kobayashi T. 2003. Cross-Coupling Reactions of (1-Fluorovinyl)methydiphenylsilane1 with Aryl Halides and Aryl Triflates. J. Org. Chem. 68:6354-9
Hanamoto T, Handa K, Mido T. 2002. Palladium-Catalyzed Carbonylative Coupling of Tributyl(1-fluorovinyl)stannane with Aryl Halides and Aryl Triflates. B. Chem. Soc. Jpn. 75:2497-502
Narumi T, Tomita K, Inokuchi E, Kobayashi K, Oishi S, et al. 2007. Facile Synthesis of Fluoroalkenes by Palladium-Catalyzed Reductive Defluorination of Allylic gem-Difluorides. Org. Lett. 9:3465-8
Pigeon X, Bergeron M, Barabé F, Dubé P, Frost HN, Paquin J-F. 2010. Activation of Allylic C–F bonds: Palladium-Catalyzed Allylic Amination of 3,3-Difluoropropenes. Angew. Chem. Int. Ed. 49:1123-7
Zhang H, Zhou C-B, Chen Q-Y, Xiao J-C, Hong R. 2011. Monofluorovinyl Tosylate: A Useful Building Block for the Synthesis of Terminal Vinyl Monofluorides via Suzuki−Miyaura Coupling. Org. Lett. 13:560-3
Uno H, Semba F, Tasaka T, Suzuki H. 1989. A Novel Generation and Behavior of Alkylfluorocarbenoids from α,α-Chlorofluoroalkyl Sulfoxides. Chem. Lett. 18:309-12
Uno H, Sakamoto K, Semba F, Suzuki H. 1992. Behaviors of α-Fluorocarbenoids Derived from the Nucleophilic Desulfinylation of α-Chloro-α-fluoroalkyl Sulfoxides. B. Chem. Soc. Jpn. 65:210-7
Tredwell M, Preshlock SM, Taylor NJ, Gruber S, Huiban M, et al. 2014. A General Copper-Mediated Nucleophilic 18F Fluorination of Arenes. Angew. Chem. Int. Ed. 53:7751-5
Makaravage KJ, Brooks AF, Mossine AV, Sanford MS, Scott PJH. 2016. Copper-Mediated Radiofluorination of Arylstannanes with [18F]KF. Org. Lett. 18:5440-3
McCarthy JR, Matthews DP, Barney CL. 1990. A new synthesis of 2-fluoro-1-olefins. Tetrahedron Lett. 31:973-6
Usuki Y, Iwaoka M, Tomoda S. 1992. A new synthesis of [small alpha]-fluoro-[small alpha],[small beta]-unsaturated ketones and esters based on organoselenium methodology. J. Chem. Soc. Chem. Commun.:1148–50
Tius MA, Kawakami JK. 1995. The reaction of XeF2 with trialkylvinylstannanes: Scope and some mechanistic observations. Tetrahedron 51:3997-4010
Furuya T, Ritter T. 2009. Fluorination of Boronic Acids Mediated by Silver(I) Triflate. Org. Lett. 11:2860-3
Li Y, Liu X, Ma D, Liu B, Jiang H. 2012. Silver-Assisted Difunctionalization of Terminal Alkynes: Highly Regio- and Stereoselective Synthesis of Bromofluoroalkenes. Adv. Synth. Catal. 354:2683-8
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Weng, Z. (2020). Transition Metal-Mediated Fluorination with Electrophilic/Nucleophilic Fluorinating Agents. In: Hu, J., Umemoto, T. (eds) Fluorination. Synthetic Organofluorine Chemistry. Springer, Singapore. https://doi.org/10.1007/978-981-10-3896-9_29
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