Frustrated Lewis Pairs
Frustrated Lewis Pairs
Frustrated Lewis Pairs
Jean-Baptiste Gualtierotti
Concept
O P
F B
F B
F
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
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
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
O
B(C6F5)
N O
O
B(C6F5)
O Base
O
B(C6F5)
P O
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
Tethered variant
H2 R
R P B (C6F5)2 P B (C6F5)2
R R
H H
Computational studies
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
Mechanism
Studies show two pathways
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
Catalyst
Scope
- Synthetic use under developed: Substitution of activated positions to form new structures?