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Organofunctional Silanes Aryne Precursors ISO 9001:2008 DIN EN ISO 9001 abcr offers a large variety of ortho-(trimethylsilyl)aryl triflates, including substituted benzyne precursors, polycyclic aryne precursors and bisaryne precursors. OTf TMS CsF MeCN rt O Ar R R2 N R1 R3 CO2R Ar R N O R O R1 CO2R2 . etc Gute Chemie R1 R2 Ts N R1 R2 N N R R O O N N N R CONR2 O Ar O R2 N N R1 NR1 R2 R3 orto-(Trimethylsilyl)aryl triflates: arynes under mild reaction conditions for synthesis The use of arynes in organic synthesis has under- gone a remarkable revival over the past few years. The key to this resurgence is the use of a method for the generation of benzyne and its derivatives under mild reaction conditions. In particular, fluo- ride-induced decomposition of orto-(trimethylsilyl) aryl triflates allows the generation of arynes in high yields, under neutral reaction conditions at mode- rate temperatures. As a result, this method has proved to be extremely useful in the synthesis of natural products, the preparation of large aromatic compounds, or the synthesis of heterocycles. Figure 1. Some examples of structures that can be obtained in one pot from orto-(trimethylsilyl)aryl triflates via benzyne chemistry (in red the new bonds). SSiOFFFOO
AB357112 1,1‘-[2,6-Bis(trimethylsilyl)-naphthalenediyl]-1,5- bis(triflate) 1364700-07-1 OTf TMS AB357100 3,6-Bis(trimethylsilyl)-2,7-naphthalenediyl-bis- trifluoromethanesulfonate 947488-89-3 TMS OTf TfO OTf TMS TMS AB391661 1,4-Bis(trimethylsilyl)phenyl-2,5-bis(triflate) 613676-07-6 TfO TMS AB357095 1,3-Bis(trimethylsilyl)phenyl-4,6-bis(triflate) AB357097 4-Chloro-2-(trimethylsilyl)phenyl trifluoro- methanesulfonate 262373-16-0 AB357094 2,4-Dibromo-6-(trimethylsilyl)phenyl trifluoro- methanesulfonate AB357098 4,5-Difluoro-2-(trimethylsilyl)phenyl trifluoro- methanesulfonate 217813-00-8 AB261551 4,5-Dimethoxy-2-(trimethylsilyl)phenyl trifluoro- methanesulfonate; 90% 866252-52-0 AB357111 9,14-Diphenyl-12-(trimethylsilyl)benzo[b]tri- phenylenyl-11-triflate 1356628-47-1 TMS OTf TMS TMS TfO OTf OTf Cl TMS Br OTf Br TMS F F OTf TMS MeO OTf MeO TMS Ph Ph OTf TMS AB357091 2-Methoxy-6-(trimethylsilyl)phenyl trifluoro- methanesulfonate 881009-83-2 OMe OTf TMS Gute Chemie
AB250327 3-Methoxy-2-(trimethylsilyl)phenyl trifluoro- methanesulfonate; 95% 217813-03-1 OMe AB250325 4-Methyl-2-(trimethylsilyl)phenyl trifluoro- methanesulfonate; 98% 262373-15-9 TMS OTf OTf TMS AB357109 6,7,10,11-Tetrakis(hexyloxy)-3-(trimethylsilyl)- triphenylenyl-2-triflate 911197-61-0 OC6H13 H13C6O AB357110 6,7,10,11-Tetrakis(methoxy)-3-(trimethylsilyl)- triphenylenyl-2-triflate H13C6O OC6H13 OMe MeO OTf TMS OTf TMS OTf TMS OTf TMS OTf TMS TMS OTf MeO Ph Ph OMe Ph Ph O O AB357101 5,6,7,8-Tetraphenyl-2-(trimethylsilyl)-3-naphthyl triflate AB357099 5-(Trimethylsilyl)benzo[d][1,3]dioxol-6-yl trifluoro- methanesulfonate 717903-52-1 AB357096 6-(Trimethylsilyl)indan-5-yl triflate 458567-00-5 AB357106 1-Trimethylsilyl-7-methoxy-2-naphthyl triflate 1027548-94-2 abcr GmbH · Phone +49 721 950 61 - 0 · Fax +49 721 950 61 - 80 · www.abcr.de · info@abcr.de
AB250631 1-(Trimethylsilyl)-2-naphthyl trifluoromethane- sulfonate; 96% 252054-88-9 TMS OTf AB250632 3-(Trimethylsilyl)-2-naphthyl trifluoromethane- sulfonate; 95% 780820-43-1 AB357104 2-(Trimethylsilyl)-1-phenanthryl triflate 294183-99-6 AB357102 3-(Trimethylsilyl)-4-phenanthryl triflate 294183-97-4 AB357105 10-(Trimethylsilyl)-9-phenanthryl triflate 252054-91-4 AB357108 3-(Trimethylsilyl)-triphenylenyl-2-triflate 911197-55-2 OTf TMS OTf TMS OTf TMS OTf TMS OTf TMS In Cooperation with Diego Pena, COMMO Group, CIQus, Universidade de Santiago de Compostela Literature: 1. a) H. Pellissier, M. Santelli, Tetrahedron 2003, 59, 701; b) E. Guitián, D. Pérez, D. Peña, Top. Organomet. Chem. 2005, 14, 109; c) D. Peña, D. Pérez, E. Guitián, Angew. Chem. Int. Ed. 2006, 45, 3579; d) R. Sanz, Org. Prep. Proced. Int. 2008, 40, 215; e) T. Kitamura, Aust. J. Chem. 2010, 63, 987; f) S. S. Bhojgude, A. T. Biju, Angew. Chem. Int. Ed. 2012, 51, 1520; g) A. Bhunia, S. R. Yetra, A. T. Biju, Chem. Soc. Rev. 2012, 41, 3140. 2. a) Y. Himeshima, T. Sonoda, H. Kobayashi, Chem. Lett. 1983, 1211; b) D. Peña, A. Cobas, D. Pérez, E. Guitián, Synthesis 2002,1454. 3. a) P. M. Tadross, B. M. Stoltz, Chem. Rev., 2012, 112, 3550; b) C. M. Gampe, E. M. Carreira, Angew. Chem. Int. Ed. 2012, 51, 3766. 4. a) D. Pérez, D. Peña, E. Guitián, Eur. J. Org. Chem. 2013, 5981; b) J. Li, Q. Zhang Synlett 2013, 24, 686; c) D. Wu, H. Ge, S. H. Liu, J. Yin, RSC Adv., DOI: 10.1039/c3ra43804j 5. a) A.V. Dubrovskiy, N. A. Markina, R. C. Larock, Org. Biomol. Chem. 2013, 11, 191. 3 . 3 1 1 1 . 9 4 2 9 6 3 Gute Chemie abcr GmbH · Im Schlehert 10, 76187 Karlsruhe · Phone +49 721 95061 - 0 · Fax +49 721 95061 - 80 · www.abcr.de · info@abcr.de