Frustrated Lewis Pairs

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Micro-topic: Frustrated Lewis Pairs

Group Meeting LSPN 26.06.2012

Jean-Baptiste Gualtierotti
Concept

Steric hindrance stops formation of adduct:

Result: Strong unquenched, «frustrated» Lewis acid


and strong unquenched Lewis base coexist

O P

F B
F B
F

Opening for novel reactivity


Discovery Timeline
1923
Definition of Lewis acids and bases in by Gilbert Lewis

Propagation of use in organic chemistry


Based on the acid/base reaction for the formation of adducts

1942 Effect of steric hindrance within adduct


noticed by Brown

1959
Wittig, Benz and then
Tochtemann noticed similar
1966 anomalies

G.N. Lewis, Valence and the Structure of Atoms and Molecules 1923 142.
G. Wittig, E. Benz, Chem. Ber. 1959, 92, 1999 – 2013.
H. C. Brown, H. I. Schlesinger, S. Z. Cardon, J. Am. Chem. Soc. 1942, 64, 325 – 329.
W. Tochtermann, Angew Chem. Int. Ed. Engl. 1966, 5, 351 – 371.
Discovery Timeline
1978 -1990 Gutmann published his analysis of the interaction of Lewis acids and bases

2000 Scott Denmark capitalizes on the principle of Gutmann

2006 Stephan Douglas encounters same phenomena as Brown


2008 Stephan formalizes the concept
From then on has drawn interest by certain groups as a potential novel catalyst system

T. Wynn, S. E. Denmark J. Am. Chem. Soc. 2001, 123, 6199 – 6200


2012 Gutmann, V. The Donor-Acceptor Approach to Molecular Interac-tions; Plenum Press: New York, 1978.
L. Cabrera, G. C. Welch, J. D. Masuda, P. Wei and D. W. Stephan, Inorg. Chim. Acta, 2006, 359, 3066.
D. W. Stephan Org. Biomol. Chem., 2008, 6, 1535–1539
Major players in the field
Prof Douglas W. Stephan

-Ph.D 1980 (University of Western Ontario)


-Postdoc 1980-1982 (Harvard, R.H. Holm)
-Professor  2008-present (University of Toronto )
-Assistant Professor 1982-1985 (University of Windsor)
-Promoted upto University Professor 2002-2007

Current research:
· The reactivity of  "frustrated Lewis pairs"
· B-based hydrogenation catalysis
· Main group CO2 chemistry
· P-based Lewis acids
· Transition metal mediated CO2 reduction
· New ligands derived from FLP chemistry
Major players in the field
Prof Gerhard Erker

-PhD: 1973 (Univ. Bochum, W. R. Roth)


-Postdoc (1974-75, Princeton University, M. Jones, Jr.
-Professor 1985-90 (Univ. Würzburg)
-Professor Univ. Münster 1990
Current research

Development of novel catalyst systems


Metal catalyzed polymerization reactions
Frustrated Lewis Pairs: metal-free dihydrogen activation/ activation of carbon dioxide and more
Carbon-carbon bond activation
Surface chemistry and heterogeneous catalysis
Unusual organic compounds
Bio-organometallic chemistry

Both professors often collaborated together on the subject


Concept
FLP will interact with unsubtituted systemps to form stable adducts that readily crystalise
Many studies on such systems have been made

Addition to conjugated enynes Addition to ynones


O
Ph R
R P P B (C6F5)2
B (C6F5)2 R
R O
Ph

Addition to aldehydes/ketones

With terminal alkynes slight variation of reaction conditions may yield addition or deprotonation adducts
R Ph N (C6F5)3B R
Ph N H
or
H N
B(C6F5)3 (C6F5)3B R
Ph

B-H Xu, R. A. A. Yanez, H. Nakatsuka, M. Kitamura, R. Frohlich, G Kehr, G. Erker Chem. Asian J. 2012, 7, 1347 – 1356
C. M. Momming, G. Kehr, B. Wibbeling, R. Frohlich, B. Schirmer, S. Grimme, G. Erker Angew. Chem. Int. Ed. 2010 49 2414-2417
D. W. Stephan, G. Erker Angew. Chem. Int. Ed. 2010, 49, 46 – 76
T. Voss, T. Mahdi, E. Otten, R. Frolich, G. Kehr, D. W. Stephan, G. Erker organometallics, 2012, 31, 2367-2378
Concept

Ring opening reactions


t
BuP
B(C6F5)3 B(C6F5)3
Ph (tBu)3 P
Ph

Regio-specific, B-C bond will form at the unsaturated methylene carbon


and resulting attack by phosphine at carbocation polarized site

J. G. M. Morton, M. A. Dureen, D. W. Stephan Chem. Commun., 2010, 46 , 8947–8949


Concept
Ring opening reactions

O
B(C6F5)
N O
O
B(C6F5)
O Base

O
B(C6F5)
P O

Base can be phosphines or tertiary amines

Exception lactides over hindrance prevents attack of the Lewis base and favors deprotonation for ring contraction

C. Kreitner, S. J. Geier, L. J. E. Stanlake, C. B. Caputo, D. W. Stephan Dalton Trans. 2011, 6771-6777 and references cited therein
Concept
Activation of small molecules

CO2 Trapping

NO trapping
R P B (C F )
NO R P R N 6 5 2
R P B (C6F5)2 B (C F )
R H R N 6 5 2
- benzene HO
O

2 equiv
R P B
R N (C6F5)2
O

R P B (C F )
R N 6 5 2

Clean reactions

A. J. P. Cardenas, B. J. Culotta, T. H. Warren, S. Grimme, A. Stute, R. Frhlich, G. Kehr, G. Erker Angew. Chem. Int. Ed. 2011, 123, 7709 –7713
C. M. Mmming, E. Otten, G. Kehr, R. Frhlich, S. Grimme, D. W. Stephan, G. Erker Angew. Chem. Int. Ed. 2009, 48, 6643 –6646
Applications
Activation of hydrogen

Main application of FLP: With H2 form an adduct holding poth protic and hydric centers

F F
F F B(C6F5)2
F B(C6F5)2
P F
H F
F F
F

F H F H
F B(C6F5)2 F B(C6F5)2
Me2SiHCl
P F P F H2
H H F
F

H2 release at 110 °C
H2 adsobtion at 25 °C
Air and water stable

HD scrambling between P and B positions observed at 100° probably via


F
F H
F B(C6F5)2 For H2 release:
F BH(C6F5)2
or
H H ΔH≠= 90 kJ/mol
(Me3C6H2)2 P F
H P F
H F (Me3C6H2)2 ΔS≠ = -96j/mol K
F
1st order kinetics for H2 release

G. C. Welch, R. R. San Juan, J. D. Masuda, D. W. Stephan Science, 2006, 314, 1124-1126


Applications
A second system

Tethered variant
H2 R
R P B (C6F5)2 P B (C6F5)2
R R
H H

Computational studies

Doted lines H-F hydrogen bonds Push pull electron transfer


ΔE≠= -11.5 kcal/mol vs free state ΔE≠= -26.3 kcal/mol vs free states
(1/2 compared to standard adduct)
Optimal distance for bifunctional cooperativity vs H 2

T. A. Rokob, A. Hamza, A. Stirling, T. Soos, I. Papai Angew. Chem. Int. Ed. 2008, 47, 2435 –2438
Applications
Amine base varient

H2 1 atm
B(C6F5)3 HB(C6F5)3
N 20 °C N
H H2
95%

NHC varient

V. Sumerin, F. Schulz, M. Nieger, M. Leskela, T. Repo, B. Rieger Angew. Chem. Int. Ed., 2008, 47, 6001-6003
P. A. Chase, A. L. Gille, T. M. Gilbert, D. W. Stephan Dalton Trans, 2009, 7179-7188
Applications
Reduction of imines

Works catalytically with


- Sterically encumbered imines
- Less encumbered imine/B(C6F5)3 adducts
- Nitriles/aziridines can also be reduced
- Decent yields 60 -98%

Issues: release of catalyst

Mechanism
Studies show two pathways

From imine From adduct


F H H
F B(C6F5)2 R1
N
H H R2 H
(Me3C6H2)2 P F R1
F H N
H F
R1 F B(C6F5)2
N H R2
H
Protonation
H R2 (Me3C6H2)2 P F
F

P. A. Chase, G. C. Welch, T. Jurca, D. W. Stephan Angew. Chem. Int. Ed. 2007, 46, 8050-8053
Applications
Catalytic reduction of enamines

5 examples
70-90% yields

Self reduction
R2 R2 R2
R1 R1 R1
R3 HB(C6F5)2 R3 H2 R3
H H Handful of examples
H B(C6F5)2
N N B(C6F5)2 Decent yields 50% with 5% catalyst
R4 R5 R5 R4 N H
R5 R4

R2 R2
R1 R1
R3 R3
N N
R4 R5 R4 R5

S. Schwendemann, R. Frohlich, G. Kehr, G. Erker Chem. Sci., 2011, 2, 1842–1849


P. A. Chase, G. C. Welch, T. Jurca, D. W. Stephan, Angew. Chem. Int. Ed. 2007, 46, 8050-8053.
Applications
Reduction of silyl enolates

Catalyst

Scope

H. Wang, R. Frohlich, G. Kehr, G. Erker Chem. Commun., 2008, 5966–5968


Applications

Mentioned aldehyde/ketone reduction attempts

Trapping of catalyst is main issue

S. Schwendemann, R. Frohlich, G. Kehr, G. Erker Chem. Sci., 2011, 2, 1842–1849


P. A. Chase, G. C. Welch, T. Jurca, D. W. Stephan Angew. Chem. Int. Ed. 2007, 46, 8050-8053
Conclusion
- Original reactivity due to coexistence of free Lewis acids and bases

- Activation of small molecules has led to some basic reactions

- Synthetic use under developed: Substitution of activated positions to form new structures?

- Potential uses: crystallization auxiliaries?

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