azaborine - university of texas at austingbdong.cm.utexas.edu/seminar/2016/2016-01-27.pdf · 2016....
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Azaborine
Synthesis, Structure and Reactivity
Chengpeng WangDong Group Meeting
University of Texas at Austin1/27/2016
Boron-Nitrogen Bonding
Liu, S.-Y. et. al. Angew. Chem. Int. Ed. 2012, 51, 6074-6092.
Boron-Nitrogen Bonding
Liu, S.-Y. et. al. Angew. Chem. Int. Ed. 2012, 51, 6074-6092.
Azaborines
Monocyclic azaborines
Fused polycyclic azaborinesAnd materials
13C spectrum 1H spectrum
Ashe, A. J. et. al. Organometallics 2001, 20, 5413-5418.
NMR Data of 1,2-Azaborine
Liu, S.-Y. et. al. Angew. Chem. Int. Ed. 2012, 51, 6074-6092.
Structure of 1,2-Azaborine
Liu, S.-Y. et. al. J. Am. Chem. Soc. 2008, 130, 7250-7252.
Structure of 1,2-Azaborine
Liu, S.-Y. et. al. J. Am. Chem. Soc. 2008, 130, 7250-7252.
Liu, S.-Y. et. al. Mol. Biosyst. 2009, 5, 1303-1305.
Stability of 1,2-Azaborine
O2 stability
water stability
Dewar, M. J. S. et. al. J. Am. Chem. Soc. 1964, 86, 5698-5699.
Dewar, M. J. S. et. al. J. Chem. Soc. 1958, 3073-3076.
Dewar, M. J. S. et. al. J. Chem. Soc. 1959, 2728-2730.
Early Synthetic Work
Early Synthetic Work
Dewar, M. J. S. et. al. J. Am. Chem. Soc. 1962, 84, 3782.
White, D. G. J. Am. Chem. Soc. 1963, 85, 3634-3636.
Ashe, A. J. et. al. Org. Lett. 2000, 2, 2089-2091.
Synthesis of 1,2-Azaborine
Ashe, A. J. et. al. Organometallics 2001, 20, 5413-5418.
Ashe, A. J. et. al. Org. Lett. 2000, 2, 2089-2091.
Synthesis of 1,2-Azaborine
Synthesis of 1,2-Azaborine
Liu, S.-Y. et. al. Angew. Chem. Int. Ed. 2009, 48, 973-977.
Liu, S.-Y. et. al. J. Am. Chem. Soc. 2013, 135, 12908-12913.
Synthesis of 1,2-Azaborine
About Shih-Yuan Liu
BS: Vienna University of Technology (Austria), 1995-1998.
PhD: MIT, with Prof. Gregory C. Fu, 1998-2003.
Postdoc: MIT, with Prof. Daniel G. Nocera, 2003-2006.
Assistant Professor: University of Oregon, 2006-2012.
Associate Professor: University of Oregon, 2012-2013.
Professor: Boston College, 2013-now.
Ashe, A. J. et. al. Org. Lett. 2007, 9, 679-681.
Electrophilic Substitution
Electrophilic Substitution
Ashe, A. J. et. al. Org. Lett. 2007, 9, 679-681.
Nucleophilic Substitution
Liu, S.-Y. et. al. Org. Lett. 2007, 9, 4905-4908.
Nucleophilic Substitution
Liu, S.-Y. et. al. Chem. Commun. 2010, 779-781.Liu, S.-Y. et. al. J. Am. Chem. Soc. 2013, 135, 12908-12913.
Liu, S.-Y. et. al. Angew. Chem. Int. Ed. 2011, 50, 8157-8160.
Nucleophilic Substitution
Liu, S.-Y. et. al. Angew. Chem. Int. Ed. 2011, 50, 8157-8160.
Nucleophilic Substitution
Mechanistic studies using nBuLi as nucleophile
Liu, S.-Y. et. al. Angew. Chem. Int. Ed. 2011, 50, 8157-8160.
Nucleophilic Substitution
Mechanistic studies using NaOtBu as nucleophile
Liu, S.-Y. et. al. Angew. Chem. Int. Ed. 2010, 49, 7444-7447.
1,2-Azaborine Cation
Liu, S.-Y. et. al. Organometallics 2011, 30, 52-54.
1,2-Azaborine Cation
Liu, S.-Y. et. al. Angew. Chem. Int. Ed. 2013, 52, 9316-9319.
Functionalization of 1,2-Azaborine
Liu, S.-Y. et. al. Org. Lett. 2014, 16, 3340-3343.
Functionalization of 1,2-Azaborine
Liu, S.-Y. et. al. J. Am. Chem. Soc. 2015, 137, 5536-5541.
Functionalization of 1,2-Azaborine
Liu, S.-Y. et. al. J. Am. Chem. Soc. 2015, 137, 5536-5541.
Functionalization of 1,2-Azaborine
Liu, S.-Y. et. al. J. Am. Chem. Soc. 2015, 137, 8932-8935.
Functionalization of 1,2-Azaborine
Liu, S.-Y. et. al. Angew. Chem. Int. Ed. 2015, 54, 7823-7827.
Diels-Alder Reaction
Liu, S.-Y. et. al. J. Am. Chem. Soc. 2010, 132, 16430-16432.
BN-Indole
Liu, S.-Y. et. al. J. Am. Chem. Soc. 2010, 132, 16430-16432.
BN-Indole
Liu, S.-Y. et. al. J. Am. Chem. Soc. 2011, 133, 11508-11511.
BN-Indole
Liu, S.-Y. et. al. J. Am. Chem. Soc. 2011, 133, 20152-20155.
1,3-Azaborine
Liu, S.-Y. et. al. J. Am. Chem. Soc. 2011, 133, 20152-20155.
1,3-Azaborine
Benzene, 120 oC
2.2 : 1
Pd/C (5 mol%)
94% total yield
Liu, S.-Y. et. al. Angew. Chem. Int. Ed. 2013, 52, 7527-7531.
1,3-Azaborine
Braunschweig, H. et. al. Angew. Chem. Int. Ed. 2012, 51, 10034-10037.
1,4-Azaborine
Liu, S.-Y. et. al. Angew. Chem. Int. Ed. 2014, 53, 6795-6799.
1,4-Azaborine
Liu, S.-Y. et. al. Angew. Chem. Int. Ed. 2015, 54, 11191-11195.
Polymerization
DPn = 12, D = 1.40
Metthews, B. W.; Liu, S.-Y. et. al. Angew. Chem. Int. Ed. 2009, 48, 6817-6819.
Biological Research
Hydrophobic pocket of the L99A mutant of T4 lysozyme
Liu, S.-Y.; Heider, J. et. al. Angew. Chem. Int. Ed. 2013, 52, 2599-2601.
Biological Research
Strong inhibitors for the hydroxylation of ethylbenzene by ethylbenzene dehydrogenase (EbDH)
Liu, S.-Y. et. al. J. Am. Chem. Soc. 2010, 132, 3289-3291.
Hydrogen Storage Potential
Liu, S.-Y. et. al. J. Am. Chem. Soc. 2010, 132, 3289-3291.
Hydrogen Storage Potential
Liu, S.-Y. et. al. J. Am. Chem. Soc. 2011, 133, 13006-13009.
Hydrogen Storage Potential
Liu, S.-Y. et. al. J. Am. Chem. Soc. 2011, 133, 19326-19329.
Hydrogen Storage Potential
Liu, S.-Y. et. al. J. Am. Chem. Soc. 2015, 137, 134-137.
Hydrogen Storage Potential
Liu, S.-Y. et. al. J. Am. Chem. Soc. 2015, 137, 134-137.
Hydrogen Storage Potential
Summary
Synthesis and reactivity research towards azaborinesremain under-developed.
Azaborines have potential applications in materials, hydrogen storage and biological researches.
Thank you for your attention!
Key #1
Key #2
Key #3
Ashe, A. J. et. al. Organometallics 2001, 20, 5413-5418.