Synthesis, Table of Contents Synthesis 2023; 55(11): 1690-1699DOI: 10.1055/a-1970-4520 paper Special Issue dedicated to Prof. Cristina Nevado, recipient of the 2021 Dr. Margaret Faul Women in Chemistry Award Versatile Synthesis of Trisphosphines Bearing Phenylene and Vinylene Backbones Useful for Metal Catalysis and Materials Applications Takahiro Doba , Shota Fukuma , Rui Shang ∗ , Eiichi Nakamura∗ Recommend Article Abstract Buy Article All articles of this category Abstract Trisphosphines, in which two phenylene or vinylene backbones connect three phosphine atoms, belong to an emerging class of ligands in metal-catalyzed organic synthesis and materials applications. However, these ligands were previously known only in a small variety because of the synthetic limitations. We report herein two versatile synthetic routes to a hitherto unavailable variety of trisphosphines. The compounds bearing phenylene backbones were synthesized by sequential addition of two different organolithium reagents to triphenyl phosphite and that with vinylene backbones by stereoretentive addition of lithium diarylphosphide to a cis-bromoalkene. The new trisphosphine compounds will serve as valuable tools for the development of transition-metal-catalyzed reactions and functional materials. Key words Key wordsphosphine ligand - tridentate - organolithium - phenylene backbone - vinylene backbone - materials Full Text References References 1a Shang R, Ilies L, Nakamura E. J. Am. Chem. Soc. 2016; 138: 10132 1b Shang R, Ilies L, Nakamura E. Chem. Rev. 2017; 117: 9086 2a Buscagan TM, Oyala PH, Peters JC. Angew. Chem. Int. Ed. 2017; 56: 6921 2b Schild DJ, Peters JC. ACS Catal. 2019; 9: 4286 2c Tanabe Y, Nishibayashi Y. Coord. Chem. Rev. 2019; 389: 73 3 Chen J.-F, Li C. ACS Catal. 2020; 10: 3881 4 Liu B, Li Y, Liu Q. Chem. Catal. 2022; 2: 883 5a Doba T, Ilies L, Sato W, Shang R, Nakamura E. Nat. Catal. 2021; 4: 631 5b Lin H.-S, Doba T, Sato W, Matsuo Y, Shang R, Nakamura E. Angew. Chem. Int. Ed. 2022; 61: e202203949 6a Lee HM, Bianchini C, Jia G, Barbaro P. Organometallics 1999; 18: 1961 6b Korstanje TJ, Ivar van der Vlugt J, Elsevier CJ, de Bruin B. Science 2015; 350: 298 6c Liao Q, Saffon-Merceron N, Mézailles N. ACS Catal. 2015; 5: 6902 6d Deng L, Kang B, Englert U, Klankermayer J, Palkovits R. ChemSusChem 2016; 9: 177 6e Adam R, Bheeter CB, Jackstell R, Beller M. ChemCatChem 2016; 8: 1329 6f Chen J.-F, Li C. Org. Lett. 2018; 20: 6719 6g Chandrashekhar VG, Baumann W, Beller M, Jagadeesh RV. Science 2022; 376: 1433 7 Zhang J, Duan C, Han C, Yang H, Wei Y, Xu H. Adv. Mater. 2016; 28: 5975 8a Shang R, Ilies L, Asako S, Nakamura E. J. Am. Chem. Soc. 2014; 136: 14349 8b Shang R, Ilies L, Nakamura E. J. Am. Chem. Soc. 2015; 137: 7660 8c Ilies L, Ichikawa S, Asako S, Matsubara T, Nakamura E. Adv. Synth. Catal. 2015; 357: 2175 8d Asako S, Ilies L, Nakamura E. J. Am. Chem. Soc. 2013; 135: 17755 8e Ilies L, Matsubara T, Ichikawa S, Asako S, Nakamura E. J. Am. Chem. Soc. 2014; 136: 13126 8f Matsubara T, Ilies L, Nakamura E. Chem. Asian J. 2016; 11: 380 8g Ilies L, Arslanoglu Y, Matsubara T, Nakamura E. Asian J. Org. Chem. 2018; 7: 1327 9 Keller J, Schlierf C, Nolte C, Mayer P, Straub BF. Synthesis 2006; 354 10 Roncali J, Blanchard P, Frère P. J. Mater. Chem. 2005; 15: 1589 11 Pirrung MC, Ghorai S. J. Am. Chem. Soc. 2006; 128: 11772 12 Matsumura K, Shimizu H, Saito T, Kumobayashi H. Adv. Synth. Catal. 2003; 345: 180 13a Duhamel L, Tombert F. J. Organomet. Chem. 1985; 280: 1 13b Suffert J, Toussaint D. J. Org. Chem. 1995; 60: 3550 14a Nelson DJ. J. Org. Chem. 1984; 49: 2059 14b Köbrich G, Akhtar A, Ansari F, Breckoff WE, Büttner H, Drischel W, Fischer RH, Flory K, Fröhlich H, Goyert W, Heinemann H, Hornke I, Merkle HR, Trapp H, Zündorf W. Angew. Chem., Int. Ed. Engl. 1967; 6: 41 15 Ilies L, Itabashi Y, Shang R, Nakamura E. ACS Catal. 2017; 7: 89 16 Afanasiev VV, Beletskaya IP, Kazankova MA, Efimova IV, Antipin MU. Synthesis 2003; 2835 17 Huang X, Zhang C, Lu X. Synthesis 1995; 769 18a Hérault D, Nguyen DH, Nuel D, Buono G. Chem. Soc. Rev. 2015; 44: 2508 18b Li P, Wischert R, Métivier P. Angew. Chem. Int. Ed. 2017; 56: 15989 19 Still WC, Kahn M, Mitra A. J. Org. Chem. 1978; 43: 2923 20 Pangborn AB, Giardello MA, Grubbs RH, Rosen RK, Timmers FJ. Organometallics 1996; 15: 1518 21 Cheng X, Peng Y, Wu J, Deng G.-J. Org. Biomol. Chem. 2016; 14: 2819 22 Jin M, Nakamura M. Chem. Lett. 2013; 42: 1035 Supplementary Material Supplementary Material Supporting Information CIF File
