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.