IT TAKES TWO TO TANGO: RECENT ADVANCES IN HOMOGENEOUS COOPERATIVE DUAL CATALYSIS BY TRANSITION METALS

JANELLE STEVES
UNIVERSITY OF WISCONSIN-MADISON LITERATURE SEMINAR

FEBRUARY 23 RD , 2012
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WHAT IS COOPERATIVE DUAL CATALYSIS?

two catalysts present at the onset of a reaction simultaneously and selectively activate and couple two substrates

Traditional single-catalyst catalysis

Allen, A. E.; MacMillan, D. W. C. Chem. Sci. 2012, 3, 633-658 Shinde, V. S.; Gajula, B.; Patil, N. T. Org. Biomol. Chem. 2012, 10, 211-224

Cooperative dual catalysis

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COOPERATIVE DUAL CATALYSIS

COMPARISON TO OTHER DUAL CATALYTIC PROCESSES

Lee, J. M.; Na, Y.; Han, H.; Chang, S. Chem. Soc. Rev. 2004, 33, 302-312 Allen, A. E.; MacMillan, D. W. C. Chem. Sci. 2012, 3, 633-658 Shinde, V. S.; Gajula, B.; Patil, N. T. Org. Biomol. Chem. 2012, 10, 211-224

COOPERATIVE CATALYSIS
INSPIRATION FROM NATURE

Brown, K. A.; Kraut, J. Faraday Discuss. 1992, 93, 217-224 Allen, A. E.; MacMillan, D. W. C. Chem. Sci. 2012, 3, 633-658

COOPERATIVE CATALYSIS
CLASSIFICATION OF REACTIVITY
Restorative Catalysis

Cascade Catalysis

Cooperative Dual Catalysis

Lee, J. M.; Na, Y.; Han, H.; Chang, S. Chem. Soc. Rev. 2004, 33, 302-312

COOPERATIVE CATALYSIS
CLASSIFICATION OF REACTIVITY
Restorative Catalysis
kermark, B.; Ljunggren, S. O.; Bckvall, J. E. J. Am. Chem. Soc. 1979, 101, 2411-2416 Divakaruni, R.; Stille, J. K. J. Am. Chem. Soc. 1978, 100, 1303-1304

Wacker oxidation

Cascade Catalysis
Eschavarren, A. M.; Stille, J. K. J. Am. Chem. Soc. 1987, 109, 5478-5486

Stille-Kelly coupling

Cooperative Dual Catalysis

Tohda, Y.; Hagihara, N.; Sonogashira, K. Tetrahedron Lett. 1975, 16, 4467-4470

Sonogashira cross-coupling
Lee, J. M.; Na, Y.; Han, H.; Chang, S. Chem. Soc. Rev. 2004, 33, 302-312 Krti, L.; Czak, B. Strategic Applications of Named Reactions in Organic Synthesis; 1st ed.; Elsevier: Burlington, 2005, p. 424, 440, 474

COOPERATIVE DUAL CATALYSIS

CATALYST PAIRING

acid-base Brnsted acid-transition metal Lewis acid-Lewis acid

organocatalyst-organocatalyst

organocatalyst-transition metal

transition metal-transition metal

Whats in a name?

Different names, similar mechanisms

Cooperative dual catalysis
Sammis, G. M.; Danjo, H.; Jacobsen, E. N. J. Am. Chem. Soc. 2004, 126, 9928-9929

Synergistic catalysis
Simonovich, S. P.; Van Humbeck, J. F.; MacMillan, D. W. C. Chem. Sci. 2012, 3, 58-61

Contemporaneous dual catalysis

Luan, X.; Trost, B. M. J. Am. Chem. Soc. 2011, 133, 1706-1709

Catalyzed catalysis
Shi, Y.; Roth, K. E.; Ramgren, S. D.; Blum. S. A. J. Am. Chem. Soc. 2009, 131, 18022-18023

Whats in a name?

Different names, similar mechanisms

Cooperative dual catalysis = Catalyzed catalysis = Synergistic catalysis = Contemporaneous dual catalysis
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COOPERATIVE DUAL CATALYSIS

GUIDING PRINCIPLES FOR DEVELOPMENT

catalyst self-quenching ligand lability bimetallic complex formation

substrate-catalyst selectivity

competition with stoichiometric substrate

intermediate affinity rates of formation rates of decomposition

Cooperative dual catalysis can be a conceptual framework for reaction design

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COOPERATIVE DUAL CATALYSIS

INSPIRATION AND EARLY EXAMPLES
Castro-Stephens reaction
Stephens, R. D.; Castro, C. E. J. Org. Chem. 1963, 28, 3313-3315

irreproducible yields

Sonogashira reaction
Tohda, Y.; Hagihara, N.; Sonogashira, K. Tetrahedron Lett. 1975, 16, 4467-4470

milder conditions near room temperature rigorously dry solvent not required functional group-tolerant avoids stoichiometric alkynylcuprate first example of cooperative dual catalysis

Can this mechanism serve as a model for the design of other cross-coupling reactions?
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BETTER TOGETHER: PALLADIUM + COPPER

BEYOND THE SONOGASHIRA REACTION

Rodrguez, N.; Melzer, B.; Linder, C; Deng, G.; Levy, L. M.; Gooen, L. J. J. Am. Chem. Soc. 2007, 129, 4824-4833

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BETTER TOGETHER: PALLADIUM + COPPER

COOPERATION FOR BIARYL CROSS-COUPLING
Design by mechanism

Schambach, R. A.; Cohen, T. J. Am. Chem. Soc. 1970, 92, 3189-3190 Nilsson, M. Acta. Chem. Scand. 1966, 20, 423-426

DFT calculations: B3LYP/6-31G* (C, H, N, O, F) ECP10MDF (Cu)

Influence of ortho coordinating groups confirmed by experimentation

Thiel, W. R.; Rodrguez, N.; Linder, C.; Melzer, B.; Gooen, L. J. Adv. Synth. Catal. 2007, 349, 2241-2246

coupling two catalytic processes

Deng, G.; Levy, L. M.; Gooen, L. J. Science 2006, 313, 662-664

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BETTER TOGETHER: PALLADIUM + COPPER

COOPERATION FOR BIARYL CROSS-COUPLING

Deng, G.; Levy, L. M.; Gooen, L. J. Science 2006, 313, 662-664

Expanded

using Ag2CO3 at lower temperatures microwave chemistry

aryl triflates meta or para groups on aryl carboxylate 14

Linder, C.; Rodrguez, N; Gooen, L. J. J. Am. Chem. Soc. 2008, 130, 15248-15249 Zimmermann, B.; Linder, C.; Rodrguez, N; Lange, P. P.; Hartung, J.; Gooen, L. J. Adv. Synth. Catal. 2009, 351, 2667-2674 Linder, C.; Rodrguez, N.; Lange, P. P.; Fromm, A.; Gooen, L. J. Chem. Commun. 2009, 7173-7175

BETTER TOGETHER: PALLADIUM + COPPER

COOPERATION FOR BIARYL CROSS-COUPLING
L = phenanthroline, phosphine, others X = I, Br, Cl

no reaction with Pd or Cu alone

proposed mechanism
transmetalation oxidative addition

decarboxylation

anion exchange

reductive elimination
Deng, G.; Levy, L. M.; Gooen, L. J. Science 2006, 313, 662-664

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UNEXPECTED COOPERATION

PALLADIUM-PALLADIUM COOPERATIVE DUAL CATALYSIS

Campeau, L.-C.; Rousseaux, S.; Fagnou, K. J. Am. Chem. Soc. 2005, 127, 18020-18021

expected major product

SEAr mechanism? Initial mechanistic study: concerted metalation-deprotonation

DFT analysis: B3LYP/TZVP B3LYP/DZVP (Pd)

Gorelsky, S. I.; Lapointe, D.; Fagnou, K. J. Am. Chem. Soc. 2008, 130, 10848-10849

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UNEXPECTED COOPERATION

COOPERATIVE DUAL CATALYSIS IN DIRECT ARYLATION

induction period observed 1st order

2 0th order

no induction period

Does cyclometalated complex do C-H activation?

1/2 order
Tan, Y.; Barrios-Landeros, F.; Hartwig, J. F. J. Am. Chem. Soc. 2012, DOI: 10.1021/ja2122156

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UNEXPECTED COOPERATION

COOPERATIVE DUAL CATALYSIS IN DIRECT ARYLATION

1

rate does not depend on 1

turnover-limiting C-H activation occurs with 2

2
calculated G
PyO-1

rate increases with increasing [2]

= 33 kcal/mol G
PyO-2

= 25 kcal/mol (experimental 27 kcal/mol)

Is PtBu3 or OAc ligand involved in C-H activation?

1 acetate involved in C-H cleavage Is transmetalation between 1 and 2 feasible? cooperative dual catalysis
1
Tan, Y.; Barrios-Landeros, F.; Hartwig, J. F. J. Am. Chem. Soc. 2012, DOI: 10.1021/ja2122156

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UNEXPECTED COOPERATION
transmetalation supported by model study oxidative addition 1

COOPERATIVE DUAL CATALYSIS IN DIRECT ARYLATION

acetate involved in C-H cleavage

turnover-limiting C-H activation 2

reductive elimination

1/2 order

1st order

Tan, Y.; Barrios-Landeros, F.; Hartwig, J. F. J. Am. Chem. Soc. 2012, DOI: 10.1021/ja2122156

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SUMMARY

COOPERATIVE DUAL CATALYZED CROSS-COUPLING

Sonogashira is a good mechanistic model What is the significance of the Pd/Cu pair? Can other metals be substituted for Pd?

Cooperative dual catalysis can result in Improved reactivity Reduced side reactions and reduced catalyst poisoning

Cooperative dual catalysis cannot always be predicted

Mechanistic study reveals greater insight into reactions
Spur development of other transformations
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COOPERATIVE DUAL CATALYSIS

USING TSUJI-TROST ELECTROPHILES

complexation decomplexation

oxidative addition nucleophilic attack

Frost, C. G.; Howart, J.; Williams, J. M. J. Tetrahedron: Asymmetry 1992, 3, 1089-1122 Krti, L.; Czak, B. Strategic Applications of Named Reactions in Organic Synthesis; 1st ed.; Elsevier: Burlington, 2005, p. 458

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COOPERATIVE DUAL CATALYSIS

USING TSUJI-TROST ELECTROPHILES

decomplexation

complexation

oxidative addition nucleophilic attack

Frost, C. G.; Howart, J.; Williams, J. M. J. Tetrahedron: Asymmetry 1992, 3, 1089-1122 Krti, L.; Czak, B. Strategic Applications of Named Reactions in Organic Synthesis; 1st ed.; Elsevier: Burlington, 2005, p. 458

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COOPERATIVE DUAL CATALYSIS

reaction design

EARLY EXAMPLES WITH TSUJI-TROST ELECTROPHILES

optimized method
additional substrates

control experiments

Pd has no effect on enantioselectivity

electron-rich ligands increase rate of Nu attack
Sawamura, M.; Sudoh, M.; Ito, Y. J. Am. Chem. Soc. 1996, 118, 3309-3310

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COOPERATIVE DUAL CATALYSIS

oxidative addition nucleophilic attack

EARLY EXAMPLES WITH TSUJI-TROST ELECTROPHILES

coordination-deprotonation

Does ligand speciation influence %ee?

decomplexation

Sawamura, M.; Sudoh, M.; Ito, Y. J. Am. Chem. Soc. 1996, 118, 3309-3310

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A GOLDEN OPPORTUNITY
reaction design

NOVEL REACTIVITY WITH GOLD AND PALLADIUM

optimized conditions

Is the mechanistic design truly operative?

Shi, Y.; Roth, K. E.; Ramgren, S. D.; Blum. S. A. J. Am. Chem. Soc. 2009, 131, 18022-18023

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A GOLDEN OPPORTUNITY
PROPOSED MECHANISM

Observed by 1H NMR spectroscopy

oxidative addition

ID by MS and competition studies reductive elimination

Saturation kinetics in substrate suggest pre-equilibrium

transmetalation

Shi, Y.; Roth, K. E.; Ramgren, S. D.; Blum. S. A. J. Am. Chem. Soc. 2009, 131, 18022-18023

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COOPERATIVE DUAL CATALYSIS

mechanistic hypothesis

OVERCOMING CHALLENGES IN SYNTHETIC CHEMISTRY

Meyer-Schuster

affinity of intermediates for each other vs. affinity for substrate

optimized conditions

Luan, X.; Trost, B. M. J. Am. Chem. Soc. 2011, 133, 1706-1709 Luan, X.; Miller, Y.; Trost, B. M. J. Am. Chem. Soc. 2011, 133, 12824-12833

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IS IT REALLY COOPERATIVE CATALYSIS?

QUALITATIVE EXPERIMENTS

system sensitive to catalyst ratios! rates matter!

Luan, X.; Trost, B. M. J. Am. Chem. Soc. 2011, 133, 1706-1709 Luan, X.; Miller, Y.; Trost, B. M. J. Am. Chem. Soc. 2011, 133, 12824-12833

28

IS IT REALLY COOPERATIVE CATALYSIS?

QUALITATIVE EXPERIMENTS

Is sequential catalysis operating?

Is palladium necessary?

Luan, X.; Trost, B. M. J. Am. Chem. Soc. 2011, 133, 1706-1709 Luan, X.; Miller, Y.; Trost, B. M. J. Am. Chem. Soc. 2011, 133, 12824-12833

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PROPOSED MECHANISM
L1 = OSiPh3 L2 =

desired product

rearrangement

oxidative addition

side product
Luan, X.; Trost, B. M. J. Am. Chem. Soc. 2011, 133, 1706-1709 Luan, X.; Miller, Y.; Trost, B. M. J. Am. Chem. Soc. 2011, 133, 12824-12833

side product

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SUMMARY

COOPERATIVE DUAL CATALYZED ALLYLATIONS

Judicious pairing of electrophile and nucleophile required Need reliable intermediates
Tsuji-Trost

Cooperative dual catalysis provides: Improved reactivity Novel reactivity Reduced side reactions and reduced catalyst poisoning Qualitative mechanistic studies provide insight Kinetics and stoichiometric studies will expand scope of reactivity

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COOPERATIVE DUAL CATALYSIS

GUIDING PRINCIPLES AND CONCLUSIONS

catalyst self-quenching ligand lability bimetallic complex formation

substrate-catalyst selectivity

competition with stoichiometric substrate

intermediate affinity rates of formation rate of decomposition

Ideal reaction: atom economical, few steps, readily available materials, selective
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THE FUTURE OF THE FIELD

Rigorous mechanistic studies Kinetics
Spectroscopy

Stoichiometric studies Control experiments Expansion of methodology to other mechanistically welldefined systems Using reliable intermediates Broadening cooperative Tsuji-Trost chemistry
Expanding scope of nucleophiles Tuning regioselectivity with ligands

Using cooperative dual catalysis as conceptual framework for reaction design Beyond palladium
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ACKNOWLEDGEMENTS
Prof. Shannon Stahl Kat Myhre Stahl group Landis group Practice Talk Attendees:
Colin Anson Jackie Brown Megan Cismesia
Tianning Diao David Mannel Jared Rigoli

Dr. James Gerken Jodie Greene Dr. Wan Pyo Hong Dr. Jessica Hoover
Andrei Iosub

Sara Moyer Alicia Phelps Dr. Adam Powell Dr. Doris Pun
Dr. Ali Rahimi

Alison Suess Dian Wang Adam Weinstein Paul White

Dr. Changwu Zheng
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Jon Jaworski

Joanne Redford