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Janelle Steves University of Wisconsin-Madison Literature Seminar February 23 rd , 2012 PowerPoint PPT Presentation


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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. What is Cooperative dual catalysis?. Traditional single-catalyst catalysis.

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Janelle Steves University of Wisconsin-Madison Literature Seminar February 23 rd , 2012

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Janelle steves university of wisconsin madison literature seminar february 23 rd 2012

It takes twoto tango:recent advances in homogeneous cooperative dual catalysis by transition metals

Janelle Steves

University of Wisconsin-Madison

Literature Seminar

February 23rd, 2012


What is cooperative dual catalysis

What is Cooperative dual catalysis?

Traditional single-catalyst catalysis

Cooperative dual catalysis

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

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 comparison to other dual catalytic processes

Cooperative dual catalysiscomparison 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

Cooperative catalysisInspiration 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

Cooperative catalysisClassification 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 reactivity1

Cooperative catalysisClassification of reactivity

Restorative Catalysis

Åkermark, B.; Ljunggren, S. O.; Bäckvall, 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

Kürti, L.; Czakó, B. Strategic Applications of Named Reactions in Organic Synthesis; 1st ed.; Elsevier: Burlington, 2005, p. 424, 440, 474


Cooperative dual catalysis catalyst pairing

Cooperative Dual CatalysisCatalyst Pairing

acid-base

Brønsted acid-transition metal

Lewis acid-Lewis acid

organocatalyst-transition metal

organocatalyst-organocatalyst

transition metal-transition metal


What s in a name different names similar mechanisms

What’s 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


What s in a name different names similar mechanisms1

What’s in a name?Different names, similar mechanisms

Cooperative dual catalysis

=

Catalyzed catalysis

=

Synergistic catalysis

=

Contemporaneous dual catalysis


Cooperative dual catalysis guiding principles for development

Cooperative dual catalysisGuiding principles for development

catalyst self-quenching

ligand lability

bimetallic complex formation

substrate-catalyst selectivity

intermediate affinity

rates of formation

rates of decomposition

competition with stoichiometric substrate

Cooperative dual catalysis can be a conceptual framework for reaction design


Cooperative dual catalysis inspiration and early examples

Cooperative Dual CatalysisInspiration 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?


Better together palladium copper beyond the sonogashira reaction

Better together: Palladium + Copperbeyond the Sonogashira reaction

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


Better together palladium copper cooperation for biaryl cross coupling

Better Together: Palladium + CopperCooperation 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.; Rodríguez, N.; Linder, C.; Melzer, B.; Gooβen, L. J. Adv. Synth. Catal.2007, 349, 2241-2246

coupling two catalytic processes

Deng, G.; Levy, L. M.; Gooβen, L. J. Science2006, 313, 662-664


Better together palladium copper cooperation for biaryl cross coupling1

Better Together: Palladium + CopperCooperation for biarylcross-coupling

Deng, G.; Levy, L. M.; Gooβen, L. J. Science2006, 313, 662-664

Expanded…

using Ag2CO3 at lower temperatures aryl triflates

microwave chemistry meta or para groups on aryl carboxylate

Linder, C.; Rodríguez, N; Gooβen, L. J. J. Am. Chem. Soc. 2008, 130, 15248-15249

Zimmermann, B.; Linder, C.; Rodríguez, N; Lange, P. P.; Hartung, J.; Gooβen, L. J. Adv. Synth. Catal. 2009, 351, 2667-2674

Linder, C.; Rodríguez, N.; Lange, P. P.; Fromm, A.; Gooβen, L. J. Chem. Commun. 2009, 7173-7175


Better together palladium copper cooperation for biaryl cross coupling2

Better Together: Palladium + CopperCooperation for biarylcross-coupling

L = phenanthroline, phosphine, others

X = I, Br, Cl

no reaction with Pd or Cu alone

proposed mechanism

transmetalation

decarboxylation

oxidative addition

anion exchange

reductive elimination

Deng, G.; Levy, L. M.; Gooβen, L. J. Science2006, 313, 662-664


Unexpected cooperation palladium palladium cooperative dual catalysis

Unexpected Cooperationpalladium-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


Unexpected cooperation cooperative dual catalysis in direct arylation

Unexpected CooperationCooperative Dual Catalysis in Direct Arylation

1

induction period observed

1st order

1

2

no induction period

0th order

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


Unexpected cooperation cooperative dual catalysis in direct arylation1

Unexpected CooperationCooperative Dual Catalysis in Direct Arylation

1

turnover-limiting C-H activation occurs with 2

rate does not depend on 1

2

rate increases with increasing [2]

calculated ΔG PyO-1 = 33 kcal/mol ΔG 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


Unexpected cooperation cooperative dual catalysis in direct arylation2

Unexpected CooperationCooperative Dual Catalysis in Direct Arylation

transmetalation supported by model study

acetate involved in C-H cleavage

oxidative addition

1

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


Summary cooperative dual catalyzed cross coupling

SummaryCooperative 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


Cooperative dual catalysis using tsuji trost electrophiles

Cooperative dual catalysisUsing Tsuji-Trost electrophiles

complexation

decomplexation

oxidative addition

nucleophilic attack

Frost, C. G.; Howart, J.; Williams, J. M. J. Tetrahedron: Asymmetry1992, 3, 1089-1122

Kürti, L.; Czakó, B. Strategic Applications of Named Reactions in Organic Synthesis; 1st ed.; Elsevier: Burlington, 2005, p. 458


Cooperative dual catalysis using tsuji trost electrophiles1

Cooperative dual catalysisUsing Tsuji-Trost electrophiles

decomplexation

complexation

oxidative addition

nucleophilic attack

Frost, C. G.; Howart, J.; Williams, J. M. J. Tetrahedron: Asymmetry1992, 3, 1089-1122

Kürti, L.; Czakó, B. Strategic Applications of Named Reactions in Organic Synthesis; 1st ed.; Elsevier: Burlington, 2005, p. 458


Cooperative dual catalysis early examples with tsuji trost electrophiles

Cooperative Dual CatalysisEarly examples with Tsuji-Trost electrophiles

reaction design

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


Cooperative dual catalysis early examples with tsuji trost electrophiles1

Cooperative Dual CatalysisEarly examples with Tsuji-Trost electrophiles

oxidative addition

nucleophilic attack

coordination-deprotonation

Does ligand speciation influence %ee?

decomplexation

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


A golden opportunity novel reactivity with gold and palladium

A golden opportunityNovel reactivity with Gold and Palladium

reaction design

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


A golden opportunity proposed mechanism

A golden opportunityProposed Mechanism

Observed by 1H NMR spectroscopy

ID by MS

and competition

studies

oxidative addition

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


Cooperative dual catalysis overcoming challenges in synthetic chemistry

Cooperative Dual CatalysisOvercoming Challenges in synthetic chemistry

mechanistic hypothesis

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


Is it really cooperative catalysis qualitative experiments

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


Is it really cooperative catalysis qualitative experiments1

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


Proposed mechanism

Proposed Mechanism

L1 = OSiPh3

L2 =

desired product

oxidative addition

rearrangement

side product

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


Summary cooperative dual catalyzed allylations

SummaryCooperative 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


Cooperative dual catalysis guiding principles and conclusions

Cooperative dual catalysisGuiding principles and Conclusions

catalyst self-quenching

ligand lability

bimetallic complex formation

substrate-catalyst selectivity

intermediate affinity

rates of formation

rate of decomposition

competition with stoichiometric substrate

Ideal reaction: atom economical, few steps, readily available materials, selective


The future of the field

The Future of the field

  • Rigorous mechanistic studies

    • Kinetics

      • Spectroscopy

    • Stoichiometric studies

    • Control experiments

  • Expansion of methodology to other mechanistically well-defined 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


Acknowledgements

Acknowledgements

Prof. Shannon Stahl

Kat Myhre

Stahl group

Landis group

Practice Talk Attendees:

Colin Anson

Jackie Brown

Megan Cismesia

Tianning DiaoDavid MannelJared Rigoli

Dr. James GerkenSara MoyerAlison Suess

Jodie GreeneAlicia PhelpsDian Wang

Dr. Wan Pyo HongDr. Adam PowellAdam Weinstein

Dr. Jessica HooverDr. Doris PunPaul White

Andrei IosubDr. Ali RahimiDr. Changwu Zheng

Jon JaworskiJoanne Redford


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