Preparation of Benzonitriles, Part 4: By Electrophilic Cyanation
In this video I'll show you some strategies for the oxidative cyanation of unsubstituted arenes. This is not a very selective reaction and may require some optimization. For certain types of aromatic nitriles, though, this approach can be practical and valuable.
Oxidative cyanations can be achieved by treatment of electron-rich arenes with electrophilic cyanide cation equivalents and Lewis acids. A second strategy is the electrophilic cyanation of polar organometallics. Then, oxidized noble metal catalysts can also bring about oxidative cyanations. I'll show you examples of all three strategies, and also of the oxidative nucleophilic cyanation of pyridines at positions 2 and 4.
Further examples (patents are available at https://worldwide.espacenet.com/):
J. Org. Chem. 2022, 87, 1545-1553; Org. Lett. 2022, 24, 2125-2130 (electrochemical); 2021, 23, 2868-2872 (Ni); J. Org. Chem. 2021, 86, 15897-15905 (electrochemical); 2020, 85, 10835-10845 (Rh); 2019, 84, 1748-1756 (KSCN); Adv. Syn. Catal. 2019, 361, 5616-5625 (pyridines); 4914-4918; Tetrahedron 2019, 75, 130550; New J. Chem. 2019, 43, 9084-9089 (Cu); Chem. Eur. J. 2019, 25, 2199-2202; 2018, 24, 11288-11291 (electrochemical); Org. Chem. Front. 2018, 5, 1848-1853 (pyridines); Org. Lett. 2018, 20, 4994-4997 (Rh); J. Org. Chem. 2017, 82, 6022-6031 (Rh); J. Am. Chem. Soc. 2017, 139, 11288-11299 (hn); Chem. Eur. J. 2017, 23, 14733-14737 (pyridines); Synlett 2016, 27, 231-236 (TsCN); J. Org. Chem. 2016, 81, 6525-6534 (Ru); 2015, 80, 12588-12593 (Rh); J. Am. Chem. Soc. 2015, 137, 8704-8707; Eur. J. Org. Chem. 2015, 2023-2029 (I2); Org. Lett. 2015, 17, 2602-2605 (NIS); Ang. Chem. Int. Ed. Eng. 2014, 53, 2186-2189 (Fe); Adv. Syn. Catal. 2013, 355, 3437-3442 (I2); J. Org. Chem. 2013, 78, 9494-9498 (Cu); Org. Lett. 2013, 15, 4960-4963 (Rh); 2012, 14, 4614-4617 (Pd); 3924-3927 (Cu); Chem. Comm. 2012, 48, 3127-3129 (BrCN); Tetrahedron 2012, 68, 4588-4595; Org. Lett. 2010, 12, 1052-1055 (Pd); J. Am. Chem. Soc. 2010, 132, 11389-11391 (Ir); 10272-10274 (Pd); Syn. Comm. 2009, 39, 407-415; J. Am. Chem. Soc. 2008, 130, 10496-10497 (electrochemical); Chem. Comm. 2006, 4530-4532; Org. Lett. 2006, 8, 4331-4333 (Pd); Synthesis 2005, 993-997 (pyridines); Tetrahedron 2003, 59, 5831-5836 (PhOCN); Syn. Comm. 1990, 20, 71-84 (RSCN); Org. Syn. 1970, 50, 52 (ClO2S-NCO); 1962, 42, 30.
Видео Preparation of Benzonitriles, Part 4: By Electrophilic Cyanation канала Synthesis with Florencio Zaragoza
Oxidative cyanations can be achieved by treatment of electron-rich arenes with electrophilic cyanide cation equivalents and Lewis acids. A second strategy is the electrophilic cyanation of polar organometallics. Then, oxidized noble metal catalysts can also bring about oxidative cyanations. I'll show you examples of all three strategies, and also of the oxidative nucleophilic cyanation of pyridines at positions 2 and 4.
Further examples (patents are available at https://worldwide.espacenet.com/):
J. Org. Chem. 2022, 87, 1545-1553; Org. Lett. 2022, 24, 2125-2130 (electrochemical); 2021, 23, 2868-2872 (Ni); J. Org. Chem. 2021, 86, 15897-15905 (electrochemical); 2020, 85, 10835-10845 (Rh); 2019, 84, 1748-1756 (KSCN); Adv. Syn. Catal. 2019, 361, 5616-5625 (pyridines); 4914-4918; Tetrahedron 2019, 75, 130550; New J. Chem. 2019, 43, 9084-9089 (Cu); Chem. Eur. J. 2019, 25, 2199-2202; 2018, 24, 11288-11291 (electrochemical); Org. Chem. Front. 2018, 5, 1848-1853 (pyridines); Org. Lett. 2018, 20, 4994-4997 (Rh); J. Org. Chem. 2017, 82, 6022-6031 (Rh); J. Am. Chem. Soc. 2017, 139, 11288-11299 (hn); Chem. Eur. J. 2017, 23, 14733-14737 (pyridines); Synlett 2016, 27, 231-236 (TsCN); J. Org. Chem. 2016, 81, 6525-6534 (Ru); 2015, 80, 12588-12593 (Rh); J. Am. Chem. Soc. 2015, 137, 8704-8707; Eur. J. Org. Chem. 2015, 2023-2029 (I2); Org. Lett. 2015, 17, 2602-2605 (NIS); Ang. Chem. Int. Ed. Eng. 2014, 53, 2186-2189 (Fe); Adv. Syn. Catal. 2013, 355, 3437-3442 (I2); J. Org. Chem. 2013, 78, 9494-9498 (Cu); Org. Lett. 2013, 15, 4960-4963 (Rh); 2012, 14, 4614-4617 (Pd); 3924-3927 (Cu); Chem. Comm. 2012, 48, 3127-3129 (BrCN); Tetrahedron 2012, 68, 4588-4595; Org. Lett. 2010, 12, 1052-1055 (Pd); J. Am. Chem. Soc. 2010, 132, 11389-11391 (Ir); 10272-10274 (Pd); Syn. Comm. 2009, 39, 407-415; J. Am. Chem. Soc. 2008, 130, 10496-10497 (electrochemical); Chem. Comm. 2006, 4530-4532; Org. Lett. 2006, 8, 4331-4333 (Pd); Synthesis 2005, 993-997 (pyridines); Tetrahedron 2003, 59, 5831-5836 (PhOCN); Syn. Comm. 1990, 20, 71-84 (RSCN); Org. Syn. 1970, 50, 52 (ClO2S-NCO); 1962, 42, 30.
Видео Preparation of Benzonitriles, Part 4: By Electrophilic Cyanation канала Synthesis with Florencio Zaragoza
organic synthesis Florencio Zaragoza Dörwald side reactions nitriles cyanide benzonitriles catalysis alkyl arenes oxidative cyanation electrophilic cyanation cyanogen halides thiocyanates aryl cyanates polar organometallics N-cyanoamides malononitriles tosyl cyanide palladium cobalt chelate formation 2-cyanopyridines 4-cyanopyridines pyridine N-oxides
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14 августа 2022 г. 10:40:37
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