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 28th 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

CarbeneInsertion
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

FromCarbene
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 ofAsymmetric
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, 74917494.

Stereodivergent
Synthesis:

J. L. Stymiest, G. Dutheuil, A. Mahmood, V. K. Aggarwal, Angew. Chem. Int. Ed., 2007, 46, 74917494.

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
GeneratedFrom
Chiral Epoxide

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

Chiral Lithium
Generated
From
ChiralAzaridine

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 toForm
Quaternary
CarbonA. 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 IIICrotylation

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

ChiralAmine
FromChiral
Boron

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

UsingZweifel
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
PropargylCarbamates

B. M. Partridge, L. Chausset-Boissarie, M. Burns, A. P. Pulis, V. K. Aggarwal, Angew. Chem. Int.
Ed., 2012, 51, 11795–11799.

From
PropargylBorate
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 Allyboron

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
FormalThree carbon
Logation ofBoronic 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 theMetal catalysis
And 1,2-metallate
Migration

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

L. 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