Homologation of Boronic Esters using OrganoLithium



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Homologation of Boronic Esters using OrganoLithium Varinder Kumar Aggarwal* Angew. Chem. Int. Ed., 2014, 54, 1082 1096. Acc. Chem. Res., 2014, 47, 3174 3183 Chem. Eur. J., 2011, 17, 13124-13132. Report: Zhe Dong Advisor: Prof. Guangbin Dong March 28 th 2016 1

Varinder Kumar Aggarwal BS in chemistry, Cambridge University 1983 PHD : Prof. Stuart Warren Cambridge University 1983-1986 Prof. Gilbert Stork, Columbia University 1986-1988. Lecturer in Chemistry, Bath University, 1988-1991. Lecturer in Chemistry, Sheffield University (1991-1995) Reader in Chemistry, Sheffield University (1995-1997) Professor in Chemistry, Sheffield University (Oct. 1997-Sept. 2000). Professor in Synthetic Chemistry, Bristol University (Sept. 2000 - present). 2

First Homologation of Boronic Esters Matteson, D. S.; Ray, R. J. Am. Chem. Soc. 1980, 102, 7590 Carbene Insertion Barluenga, J.; Tomas-Gamasa, M.; Aznar, F.; Valdes, C. Nat. Chem. 2009, 1, 494 Peng, C.; Zhang, W.; Yan, G.; Wang, J. Org. Lett. 2009, 11, 1667. 3

From Carbene To yilde V. K Aggarwal, G. Yu Fang, A. Schmidt, J. Am. Chem. Soc., 2005, 127, 1642-1643.

Mechanism Containing 1,2-metallate Migration V. K Aggarwal, G. Yu Fang, A. Schmidt, J. Am. Chem. Soc., 2005, 127, 1642-1643.

Selectivity of Asymmetric Borate for 1,2-metallate Migration R. Robiette, G. Y. Fang, J. N. Harvey, V. K. Aggarwal, Chem. Commun., 2006, 741-743.

2+1 reaction : From vinyl Nuc to allyl Nuc G. Y. Fang, V. K. Aggarwal, Angew. Chem. Int. Ed., 2007, 46, 359-362..

1,3 Asymmetric Crotylation G. Y. Fang, V. K. Aggarwal, Angew. Chem. Int. Ed., 2007, 46, 359-362..

1,1 Asymmetric Crotylation G. Y. Fang, V. K. Aggarwal, Angew. Chem. Int. Ed., 2007, 46, 359-362..

Diastereoselectivity Model Asymmetric Crotylation G. Y. Fang, V. K. Aggarwal, Angew. Chem. Int. Ed., 2007, 46, 359-362..

Selectivity of 9-BBN Borate for 1,2-metallate Migration G. Y. Fang, O. A. Wallner, N. Di Blasio, X Ginesta, J. N. Harvey, V, K. Aggarwal, J. Am. Chem. Soc., 2007, 129, 14632-14639.

From Sulfur Yilde to Chiral Lithium Carbamate J. L. Stymiest, G. Dutheuil, A. Mahmood, V. K. Aggarwal, Angew. Chem. Int. Ed., 2007, 46, 7491-7494.

Stereodivergent Synthesis: J. L. Stymiest, G. Dutheuil, A. Mahmood, V. K. Aggarwal, Angew. Chem. Int. Ed., 2007, 46, 7491-7494.

From Chiral Carbamate to Chiral Boronate J. L. Stymiest, V. Bagutski, R. M. French, V. K. Aggarwal,Nature, 2008, 456, 778-782.

Explanation for Retention and Inversion J. L. Stymiest, V. Bagutski, R. M. French, V. K. Aggarwal, Nature, 2008, 456, 778-782.

Chiral Lithium Generated From Chiral Epoxide E. Vedrenne, O. A. Wallner, M. Vitale, F. Schmidt, V. K. Aggarwal,Org. Lett. 2009, 11, 165-168.

Chiral Lithium Generated From Chiral Azaridine F. Schmidt, F. Keller, E. Vedrenne, V. K. Aggarwal, Angew. Chem. Int. Ed., 2009, 48, 1149-1152.

F. Schmidt, F. Keller, E. Vedrenne, V. K. Aggarwal, Angew. Chem. Int. Ed., 2009, 48, 1149-1152.

Rh(I) catalyzed Stereospecific Transfer to Form Quaternary Carbon A. Ros, V. K. Aggarwal,Angew. Chem. Int. Ed., 2009, 48, 6289-6292.

Total Synthesis of (+)-Faranal* G. Dutheuil, M. P. Webster, P. A. Worthington, V. K. Aggarwal,Angew. Chem. Int. Ed., 2009, 48, 6317-6319.

Stereodivergent Crotylation M. Althaus, A. Mahmood, J. Ramón Suárez, S. P. Thomas, V. K. Aggarwal,J. Am.Chem.Soc., 2010, 132, 4025-4028..

Class I Crotylation M. Althaus, A. Mahmood, J. Ramón Suárez, S. P. Thomas, V. K. Aggarwal,J. Am.Chem.Soc., 2010, 132, 4025-4028..

Class II Crotylation M. Althaus, A. Mahmood, J. Ramón Suárez, S. P. Thomas, V. K. Aggarwal,J. Am.Chem.Soc., 2010, 132, 4025-4028.

Class III Crotylation M. Althaus, A. Mahmood, J. Ramón Suárez, S. P. Thomas, V. K. Aggarwal,J. Am.Chem.Soc., 2010, 132, 4025-4028.

Unusual Inversion during 1,2 metallate migration M. Binanzer, G. Y. Fang, V. K. Aggarwal,Angew. Chem. Int. Ed., 2010, 49, 4264-4268..

Unusual Inversion during 1,2 metallate migration M. Binanzer, G. Y. Fang, V. K. Aggarwal,Angew. Chem. Int. Ed., 2010, 49, 4264-4268..

Total Synthesis of Solandelactone E: V. Bagutski, R. M. French, V. K. Aggarwal,Angew. Chem. Int. Ed., 2010, 49, 5142-5145..

Improved 100% Charity Transfer V. Bagutski, R. M. French, V. K. Aggarwal,Angew. Chem. Int. Ed., 2010, 49, 5142-5145..

Stereospecific Proto-deboranlation S. Nave, R. P. Sonawane, T. G. Elford, V. K. Aggarwal.J. Am. Chem. Soc., 2010, 132, 17096-17098

Stereospecific Proto-deboranlation S. Nave, R. P. Sonawane, T. G. Elford, V. K. Aggarwal.J. Am. Chem. Soc., 2010, 132, 17096-17098

Chiral Amine From Chiral Boron V. Bagutski, T. G. Elford, V. K. Aggarwal.Angew. Chem. Int. Ed., 2011, 50, 1080-1083

Using Zweifel Olefination To work up V. K. Aggarwal, M. Binanzer, M. Carolina de Ceglie, M. Gallanti, B. W. Glasspoole, S. J. F. Kendrick, R. P. Sonawane, A. Vazquez-Romero, M. P. Webster. Org. Lett., 2011, 13, 1490-1493

In-situ Cascade to form Quaternary Carbon R. P. Sonawane, V. Jheengut, C. Rabalakos, R. Larouche-Gauthier, H. K. Scott, V. K. Aggarwal, Angew. Chem. Int. Ed., 2011, 50, 3760-3763.

In-situ Cascade to form Quaternary Carbon R. P. Sonawane, V. Jheengut, C. Rabalakos, R. Larouche-Gauthier, H. K. Scott, V. K. Aggarwal, Angew. Chem. Int. Ed., 2011, 50, 3760-3763.

R. P. Sonawane, V. Jheengut, C. Rabalakos, R. Larouche-Gauthier, H. K. Scott, V. K. Aggarwal, Angew. Chem. Int. Ed., 2011, 50, 3760-3763.

Total Synthesis of (+)-Erogorgiaene T. G. Elford, S. Nave, R. P. Sonawane, V. K. Aggarwal,J. Am. Chem. Soc., 2011, 133, 16798-16801

Total Synthesis of (+)-Erogorgiaene T. G. Elford, S. Nave, R. P. Sonawane, V. K. Aggarwal,J. Am. Chem. Soc., 2011, 133, 16798-16801

Chiral Organometallic Type Nucleophiles for Asymmetric Synthesis. A type orbital for SE2 Inservsion R. Larouche-Gauthier, T. G. Elford, V. K. Aggarwal,J. Am. Chem. Soc., 2011, 133, 16794-16797

Activating group Effect. Scope of electrophile R. Larouche-Gauthier, T. G. Elford, V. K. Aggarwal,J. Am. Chem. Soc., 2011, 133, 16794-16797

R. Larouche-Gauthier, T. G. Elford, V. K. Aggarwal,J. Am. Chem. Soc., 2011, 133, 16794-16797

OrganoLithium From Chiral Secondary Allylic Carbamates A. P. Pulis, V. K. Aggarwal,J. Am. Chem. Soc., 2012, 134, 7570-7574

Total Synthesis of C30 Botryococcene. A. P. Pulis, V. K. Aggarwal,J. Am. Chem. Soc., 2012, 134, 7570-7574

OrganoLithium From Chiral Secondary Propargyl Carbamates B. M. Partridge, L. Chausset-Boissarie, M. Burns, A. P. Pulis, V. K. Aggarwal, Angew. Chem. Int. Ed., 2012, 51, 11795 11799.

From Propargyl Borate To chiral allene B. M. Partridge, L. Chausset-Boissarie, M. Burns, A. P. Pulis, V. K. Aggarwal, Angew. Chem. Int. Ed., 2012, 51, 11795 11799.

Fine tuning Of α and γ Seletivite Protonation Of Ally boron M. J. Hesse, C. P. Butts, C. L. Willis, V. K. Aggarwal,Angew. Chem. Int. Ed., 2012, 51, 12444 12448.

D.R. Model M. J. Hesse, C. P. Butts, C. L. Willis, V. K. Aggarwal,Angew. Chem. Int. Ed., 2012, 51, 12444 12448.

A new protocol For Roush-type Aldehyde Allylation Jack L.-Y. Chen, Helen K Scott, Matthew J Hesse, Christine L. Willis, Varinder K. Aggarwal.J. Am. Chem. Soc., 2013, 135, 5316 5319

Method A, directly mix together, Method B, nbuli and TFAA activation Jack L.-Y. Chen, Helen K Scott, Matthew J Hesse, Christine L. Willis, Varinder K. Aggarwal.J. Am. Chem. Soc., 2013, 135, 5316 5319

A new protocol For Ketone Allylation Seterodivergent Synthesis Jack L.-Y. Chen, Varinder K. Aggarwal.Angew. Chem. Int. Ed., 2014, 53, 10992-10996

Ketone Allylation Jack L.-Y. Chen, Varinder K. Aggarwal.Angew. Chem. Int. Ed., 2014, 53, 10992-10996

Generate the Chiral Lithium at Unactivated Position Alexander P. Pulis, Daniel J. Blair, Eva Torres, and Varinder K. Aggarwal.JACS, 2013, 135, 16054 16057.

14 used to Need 15 steps Alexander P. Pulis, Daniel J. Blair, Eva Torres, and Varinder K. Aggarwal.JACS, 2013, 135, 16054 16057.

Transfer OH to Bpin Stefan Roesner, Christopher A. Brown, Maziar M. Mohiti, Alexander P. Pulis, Ramesh Rasappan, Daniel J. Blair, Stefanie Essafi, Daniele Leonori and Varinder K Aggarwal. Chem.Commun., 2014, 50, 4053-4055.

Quaternary Carbon Center formation Daniel J. Blair, Catherine J. Fletcher, Katherine M. P. Wheelhouse, Varinder K. Aggarwal.Angew. Chem. Int. Ed., 2014, 53, 5552 5555

Daniel J. Blair, Catherine J. Fletcher, Katherine M. P. Wheelhouse, Varinder K. Aggarwal.Angew. Chem. Int. Ed., 2014, 53, 5552 5555

Daniel J. Blair, Catherine J. Fletcher, Katherine M. P. Wheelhouse, Varinder K. Aggarwal.Angew. Chem. Int. Ed., 2014, 53, 5552 5555

1,1 di-substituted allyl Bpin in the crotylation Matthew J. Hesse, Stéphanie Essafi, Charlotte G. Watson, Jeremy N. Harvey, David Hirst, Christine L. Willis, Varinder Aggarwal. Angew. Chem. Int. Ed., 2014, 53, 6145 6149

Quaternary Carbon Center formation Amadeu Bonet, Marcin Odachowski, Daniele Leonori, Stephanie Essafi, Varinder Aggarwal. Nat. Chem., 2014, 6, 584 589

Quaternary Carbon Center formation Amadeu Bonet, Marcin Odachowski, Daniele Leonori, Stephanie Essafi, Varinder Aggarwal. Nat. Chem., 2014, 6, 584 589

Mechanism for Quaternary Carbon Center formation Amadeu Bonet, Marcin Odachowski, Daniele Leonori, Stephanie Essafi, Varinder Aggarwal. Nat. Chem., 2014, 6, 584 589

Remove the unactivate Bpin Ramesh Rasappan, Varinder Aggarwal. Nat. Chem., 2014, 6, 810 814

Ramesh Rasappan, Varinder Aggarwal. Nat. Chem., 2014, 6, 810 814

Auto-synthesis Matthew Burns, Stéphanie Essafi, Jessica R. Bame, Stephanie P. Bull, Matthew P. Webster, Sébastien Balieu, James W. Dale, Craig P. Butts, Jeremy N. Harvey, Varinder K. Aggarwal. Nature, 2014, 513, 183-188

Only three example in the paper Matthew Burns, Stéphanie Essafi, Jessica R. Bame, Stephanie P. Bull, Matthew P. Webster, Sébastien Balieu, James W. Dale, Craig P. Butts, Jeremy N. Harvey, Varinder K. Aggarwal. Nature, 2014, 513, 183-188

Vicinal Quaternary Carbon Center formation Charlotte G. Watson, Angelica Balanta, Tim G. Elford, Stéphanie Essafi, Jeremy N. Harvey, Varinder K. Aggarwal.J. Am. Chem. Soc., 2014, 136, 17370-17373

Charlotte G. Watson, Angelica Balanta, Tim G. Elford, Stéphanie Essafi, Jeremy N. Harvey, Varinder K. Aggarwal.J. Am. Chem. Soc., 2014, 136, 17370-17373

C2/C4- alkylation of pyridine Josep Llaveria, Daniele Leonori, Varinder K. Aggarwal.J. Am. Chem. Soc., 2015, 137, 10958 10961

Josep Llaveria, Daniele Leonori, Varinder K. Aggarwal.J. Am. Chem. Soc., 2015, 137, 10958 10961

Chiral fluorine compound synthesis Christopher Sandford, Ramesh Rasappan, Varinder K. Aggarwal. J. Am. Chem. Soc., 2015, 137, 10100 10103

Christopher Sandford, Ramesh Rasappan, Varinder K. Aggarwal. J. Am. Chem. Soc., 2015, 137, 10100 10103

Pd-catalyzed Formal Three carbon Logation of Boronic Esters Phillip J. Unsworth, Dr. Daniele Leonori, Varinder K. Aggarwal.Angew. Chem. Int. Ed., 2014, 53, 9846-9850

Phillip J. Unsworth, Dr. Daniele Leonori, Varinder K. Aggarwal.Angew. Chem. Int. Ed., 2014, 53, 9846-9850

Merging the Metal catalysis And 1,2-metallate Migration. Zhang, G. J. Lovinger, E. K. Edelstein, A. A. Szymaniak, M. P. Chierchia and J. P. Morken, Science, 2016, 351, 70.

. Zhang, G. J. Lovinger, E. K. Edelstein, A. A. Szymaniak, M. P. Chierchia and J. P. Morken, Science, 2016, 351, 70.

Thank you for your attention