Halogen-bonded supramolecular capsule functionalizes its guest via mechanochemical Wittig olefination Joseph M. Marrett and Tomislav Friščić McGill University Department of Chemistry, Canada The molecular inclusion of chemical species in host-guest complexes has enabled a wide set of chemical transformations including photodimerizations, 1 Diels-Alder reactions, 2 and more. 3 Most often, these reactions concern only the guest, with the host acting as an inert container for transformation. We now discuss an alternative approach to the design of solid-state reactivity, where a halogen-bonded host acts to mechanochemically functionalize its own guest in a Wittig olefination reaction, 4 producing 1,1-dihaloolefins in high yield. These pre-formulated combinations of substrate and reagent can also be used as surrogates for 1,1-diahaloolefins in a one-pot mechanochemical Wittig olefination and Sonogashira coupling 5 to produce eneynes and enediynes. These complexes of substrate and reagent are, to the best of our knowledge, a novel class of materials which could provide convenient “on-demand” synthesis of reactive, volatile, or otherwise difficult to store compounds from stable and easily stored crystalline solids. References 1. M. Yoshizawa, Y. Takeyama, T. Kusukawa, M. Fujita, Chem. Int. Ed. 2002 , 41 , 1347-1349; 2. K. Tanaka, E. Mochizuki, N. Yasui, Y. Kai, I. Miyahara, K. Hirotsu, F. Toda, Tetrahedron 2000 , 56 , 6853-6865; 3. J. N. Moorthy, K. Venkatesan, R. G. Weiss, J. Org. Chem. 1992 , 57 , 3292-3297. 4. J. Kang, J. Rebek, Nature 1997 , 385 , 50-52; 5. J. Kang, G. Hilmersson, J. Santamaría, J. Rebek, Am. Chem. Soc. 1998 , 120 , 3650-3656. 6. J. Cram, M. E. Tanner, R. Thomas, Angew. Chem. Int. Ed. Engl. 1991 , 30 , 1024-1027. 7. V. P. Balema, J. W. Wiench, M. Pruski, V. K. Pecharsky, Am. Chem. Soc. 2002 , 124 , 6244-6245; 8. K. L. Denlinger, L. Ortiz-Trankina, P. Carr, K. Benson, D. C. Waddell, J. Mack Beil. J. Org. Chem. 2018 , 14 , 688-696. 9. A. Fulmer, W. C. Shearouse, S. T. Medonza, J. Mack, Green Chem. 2009 , 11 , 1821-1825.
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