Mechanistic Studies in Copper Catalysis
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1 chanistic Studies in Copper Catalysis Jen Alleva May 1st 2013
2 Timeline of Achievements in Copper Chemistry General istorical verview first cross-couplings 1869 Ullmann Goldberg Glaser 1903 Glaser, C. Ann. D. Chemie U. Pharm, 1869, 2,
3 Timeline of Achievements in Copper Chemistry General istorical verview first cross-couplings 1869 Ullmann Goldberg Glaser 1903 Ullman, F. Ber. 1903, 36, Goldberg, I. Ber. 1906, 39,
4 Timeline of Achievements in Copper Chemistry General istorical verview first cross-couplings Ullmann Goldberg Glaser 1903 eich Gilman synthesis of first copper organometallic reagents Gilman,.; Jones,. G.; Woods, L. A. J. rg. Chem, 1952, 17,
5 Timeline of Achievements in Copper Chemistry General istorical verview first cross-couplings "Click" Chemistry Ullmann Goldberg uisgen Glaser 1903 eich Gilman 1961 Sharpless synthesis of first copper organometallic reagents uisgen,. Proc. Chem Soc., 1961,
6 Timeline of Achievements in Copper Chemistry General istorical verview first cross-couplings "Click" Chemistry Ullmann Goldberg uisgen Glaser 1903 eich Gilman 1961 Sharpless synthesis of first copper organometallic reagents Chan-Evans-Lam Cu C couplings uisgen,. Proc. Chem Soc., 1961,
7 Copper in Cross-Coupling eactions
8 Copper in Cross-Coupling eactions B u =,, S = halide nucleophile = halide oxidative coupling standard cross-coupling oxidative coupling u Chan-Evans-Lam Ullmann-Goldberg "Aromatic Glaser-ay"
9 Electronic Properties of Copper E 1/2 = 0.16V E 1/2 = 2.4V Cu I Cu II Cu III d 10 isoelectronic with i(0) d 9 d 8, metal cation isoelectronic with Pd(II) * Vs. SCE in C, Bratsch, S. G. J. Phys. Chem. ef. Data 1989, 18, 1 21
10 Electronic Properties of Copper E 1/2 = 0.16V E 1/2 = 2.4V Cu I Cu II Cu III d 10 isoelectronic with i(0) d 9 d 8, metal cation isoelectronic with Pd(II) forms shorter bonds than Pd harder Lewis acidity than Pd higher affinity for, ligands smaller coordination shell can not accomodate large ancillary ligands Beletskaya, I. P; Cheprakov, A. V. rganometallics 2012, 31, * Vs. SCE in C, Bratsch, S. G. J. Phys. Chem. ef. Data 1989, 18, 1 21
11 Electronic Properties of Copper E 1/2 = 0.16V E 1/2 = 2.4V Cu I Cu II Cu III d 10 isoelectronic with i(0) d 9 d 8, metal cation isoelectronic with Pd(II) forms shorter bonds than Pd harder Lewis acidity than Pd higher affinity for, ligands smaller coordination shell can not accomodate large ancillary ligands highly electrophilic and unstable potent oxidizer requires highly stabilizing ligands Br Cu III Beletskaya, I. P; Cheprakov, A. V. rganometallics 2012, 31, * Vs. SCE in C, Bratsch, S. G. J. Phys. Chem. ef. Data 1989, 18, 1 21
12 Electronic Properties of Copper E 1/2 = 0.16V E 1/2 = 2.4V Cu I Cu II Cu III d 10 isoelectronic with i(0) d 9 d 8, metal cation isoelectronic with Pd(II) forms shorter bonds than Pd harder Lewis acidity than Pd higher affinity for, ligands smaller coordination shell can not accomodate large ancillary ligands highly electrophilic and unstable potent oxidizer requires highly stabilizing ligands unstable towards the reverse reductive elimination can not take part in ligand exchange requires the nucleophile to be in the coordination sphere prior to oxidative addition Beletskaya, I. P; Cheprakov, A. V. rganometallics 2012, 31, * Vs. SCE in C, Bratsch, S. G. J. Phys. Chem. ef. Data 1989, 18, 1 21
13 Cross-Coupling Classifications regular cross-coupling: transition metal mediated nucleophilic substitution B M L B organic electrophile nucleophile base
14 Cross-Coupling Classifications regular cross-coupling: transition metal mediated nucleophilic substitution B M L B organic electrophile nucleophile base 1 Pd II B Pd 0 Pd 0 /Pd II 2 1 Pd II B
15 Cross-Coupling Classifications regular cross-coupling: transition metal mediated nucleophilic substitution B M L B organic electrophile nucleophile base 1 Pd II B 2 Cu I Pd 0 /Pd II Cu I /Cu III Pd Pd II 3 Cu I 2 3 Cu III B nucleophile plays the role of ancillary ligand in Cu I /Cu III
16 Cross-Coupling Classifications oxidative cross-coupling: transition metal mediated coupling of two nucleophiles 1 M organic nucleophile 2 3 M L M 2e nucleophile M
17 Cross-Coupling Classifications oxidative cross-coupling: transition metal mediated coupling of two nucleophiles 1 M organic nucleophile 2 3 M L M 2e nucleophile M 1 M Pd II 1 M 2 3 Pd II Pd II /Pd IV 2 1 Pd II Pd IV 3
18 Cross-Coupling Classifications oxidative cross-coupling: transition metal mediated coupling of two nucleophiles 1 M organic nucleophile 2 3 M L M 2e nucleophile M 1 M Pd II 1 M Cu II Pd II Pd II /Pd IV 2 1 Pd II 3 2 Cu II Cu I /Cu II /Cu III 2 3 Cu II Cu I Cu II Pd IV Cu III 1
19 Cross-Coupling Classifications inverse or Umpolung cross-coupling: transition metal mediated electrophilic substitution 1 LG 2 3 M L LG organic nucleophile electrophile nucleofugal leaving group
20 Cross-Coupling Classifications inverse or Umpolung cross-coupling: transition metal mediated electrophilic substitution 1 LG 2 3 M L LG organic nucleophile electrophile nucleofugal leaving group 2 LG LG Pd II 1 Pd 0 Pd 0 /Pd II 2 1 Pd II
21 Cross-Coupling Classifications inverse or Umpolung cross-coupling: transition metal mediated electrophilic substitution 1 LG 2 3 M L LG organic nucleophile electrophile nucleofugal leaving group 2 LG LG Pd II Cu I LG 2 3 Pd 0 /Pd II Cu I /Cu III Pd Pd II 3 Cu I 2 3 Cu III
22 Copper in Cross-Coupling eactions B u =,, S = halide nucleophile = halide oxidative coupling standard cross-coupling oxidative coupling u Chan-Evans-Lam Ullmann-Goldberg "Aromatic Glaser-ay"
23 chanistic Studies in Copper Catalysis Shannon Stahl avi ibas Ted Cohen
24 Copper in Cross-Coupling eactions B u =,, S = halide nucleophile = halide oxidative coupling standard cross-coupling oxidative coupling u Chan-Evans-Lam Ullmann-Goldberg "Aromatic Glaser-ay"
25 Chan-Evans-Lam Coupling oxidative cross-coupling B 2 equiv. Cu(Ac) 2 4Å mol sieves, 2 EtAc heteroatom boronic acid diaryl ether nucleophile Chan D. M. T.; Monaco, K. L.; Wang,.-P.; Winters, M. P. Tetrahedron Lett. 1998, 39, Evans, D. A.; Katz, J. L.; West, T.. Tetrahedron Lett. 1998, 39, Lam, P. Y. S.; Clark, C. G.; Saubern, S.; Adams, J.; Winters, M. P.; Chan, D. T., Combs, A. Tetrahedron Lett. 1998, 39, 2941.
26 Chan-Evans-Lam Coupling oxidative cross-coupling B 2 equiv. Cu(Ac) 2 4Å mol sieves, 2 EtAc heteroatom boronic acid diaryl ether nucleophile 2 Cu II Cu II Cu I /Cu II /Cu III 2 Cu II can be made catalytic with an added oxidant 2 Cu I 3 1 Cu II CEL is stoichiometric in Cu II Cu III 1
27 Chan-Evans-Lam Coupling select catalytic methods B 20 mol% [Cu() TMEDA] 2 Cl 2 C 2 Cl 2, 2, r.t. 72% Collman, J. P.; Zhong, M. rg. Lett. 2000, 2,
28 Chan-Evans-Lam Coupling select catalytic methods B 20 mol% [Cu() TMEDA] 2 Cl 2 C 2 Cl 2, 2, r.t. 72% 2 Si() equiv Cu(Ac) 2 TBAF, DMF, 2, r.t. 61% Lam, P. S.; Deudon, S.; auptman, E.; Clark, C. G. Tetrahedron Lett. 2001, 42, Collman, J. P.; Zhong, M. rg. Lett. 2000, 2,
29 Chan-Evans-Lam Coupling select catalytic methods B 20 mol% [Cu() TMEDA] 2 Cl 2 C 2 Cl 2, 2, r.t. 72% 2 Si() equiv Cu(Ac) 2 TBAF, DMF, 2, r.t. 61% 2 B 5 mol% Cu(Ac) 2 10 mol% myristic acid 2,6-lutidine, Ph, r.t. 91% Antilla, J. C.; Buchwald, S. L. rg Lett, 2001, 3, Lam, P. S.; Deudon, S.; auptman, E.; Clark, C. G. Tetrahedron Lett. 2001, 42, Collman, J. P.; Zhong, M. rg. Lett. 2000, 2,
30 Chan-Evans-Lam Coupling determining reaction stoichiometry B 5 mol% Cu(Ac) 2 1 atm 2, 27 C, 6h B() 2 () 88% 12% King, A. E.; Brunold, T. C.; Stahl. S. S. J. Am. Chem. Soc. 2009, 131,
31 Chan-Evans-Lam Coupling determining reaction stoichiometry B 5 mol% Cu(Ac) 2 1 atm 2, 27 C, 6h B() 2 () 88% 12% Cu and 2 stoichiometry determined from anaerobic single-turnover experiment Cu II /product ratio is 2:1 King, A. E.; Brunold, T. C.; Stahl. S. S. J. Am. Chem. Soc. 2009, 131,
32 Chan-Evans-Lam Coupling determining reaction stoichiometry B 5 mol% Cu(Ac) 2 1 atm 2, 27 C, 6h B() 2 () 88% 12% Cu and 2 stoichiometry determined from anaerobic single-turnover experiment result consistent with Cu oxidase mechanism Cu II /product ratio is 2:1 Cu I / 2 ratio is 4:1 King, A. E.; Brunold, T. C.; Stahl. S. S. J. Am. Chem. Soc. 2009, 131,
33 Chan-Evans-Lam Coupling initial rates experiment reveals turnover-limiting step B 5 mol% Cu(Ac) 2 1 atm 2, 27 C, 6h B() 2 () 88% 12% Initial rates experiment: suggest transmetalation as turnover-limiting King, A. E.; Brunold, T. C.; Stahl. S. S. J. Am. Chem. Soc. 2009, 131,
34 Chan-Evans-Lam Coupling initial rates experiment reveals turnover-limiting step B 5 mol% Cu(Ac) 2 1 atm 2, 27 C, 6h B() 2 () 88% 12% Initial rates experiment: suggest transmetalation as turnover-limiting 1 st order dependence on Cu(Ac) 2 saturation dependence on boronic ester King, A. E.; Brunold, T. C.; Stahl. S. S. J. Am. Chem. Soc. 2009, 131,
35 Chan-Evans-Lam Coupling initial rates experiment reveals turnover-limiting step B 5 mol% Cu(Ac) 2 1 atm 2, 27 C, 6h B() 2 () 88% 12% Initial rates experiment: suggest transmetalation as turnover-limiting 1 st order dependence on Cu(Ac) 2 Cu I oxidation is relatively fast compared to transmetalation saturation dependence on boronic ester 0 order dependence on 2 King, A. E.; Brunold, T. C.; Stahl. S. S. J. Am. Chem. Soc. 2009, 131,
36 Electron Paramagnetic esonance Spectroscopy Cu II : d 9, square planar d x 2 y 2 d xy d z 2 d yz d xz ground state
37 Electron Paramagnetic esonance Spectroscopy Cu II : d 9, square planar d x 2 y 2 d x 2 y 2 d xy d xy d z 2 d z 2 d yz d xz d yz d xz ground state coupling excited state
38 Electron Paramagnetic esonance Spectroscopy Cu II : d 9, square planar d x 2 y 2 d x 2 y 2 d x 2 y 2 d xy d xy d xy d z 2 d z 2 d z 2 d yz d xz d yz d xz d yz d xz ground state coupling excited state d z 2 does not couple orbitals have incorrect symmetry
39 Electron Paramagnetic esonance Spectroscopy Cu II : d 9, square planar d x 2 y 2 d x 2 y 2 d x 2 y 2 d xy d xy d xy d z 2 d z 2 d z 2 d yz d xz d yz d xz d yz d xz ground state coupling excited state d z 2 does not couple orbitals have incorrect symmetry g obs = g e xλ ΔE
40 Electron Paramagnetic esonance Spectroscopy Cu II : d 9, square planar d x 2 y 2 d x 2 y 2 d x 2 y 2 d xy d xy d xy d z 2 d z 2 d z 2 d yz d xz d yz d xz d yz d xz ground state coupling excited state d z 2 does not couple orbitals have incorrect symmetry g obs = g e xλ ΔE g obs : empirical value from spectrum g e : energy of free electron ( )
41 Electron Paramagnetic esonance Spectroscopy Cu II : d 9, square planar d x 2 y 2 d x 2 y 2 d x 2 y 2 d xy d xy d xy d z 2 d z 2 d z 2 d yz d xz d yz d xz d yz d xz ground state coupling excited state d z 2 does not couple orbitals have incorrect symmetry g obs = g e xλ ΔE g obs : empirical value from spectrum g e : energy of free electron ( ) x: modification factor of the free electron based on orbital mixing
42 Electron Paramagnetic esonance Spectroscopy Cu II : d 9, square planar d x 2 y 2 d x 2 y 2 d x 2 y 2 d xy d xy d xy d z 2 d z 2 d z 2 d yz d xz d yz d xz d yz d xz ground state coupling excited state d z 2 does not couple orbitals have incorrect symmetry g obs = g e xλ ΔE g obs : empirical value from spectrum g e : energy of free electron ( ) x: modification factor of the free electron based on orbital mixing λ: spin orbit coupling constant ΔE: energy between two orbitals
43 Chan-Evans-Lam Coupling initial rates experiment reveals turnover-limiting step B 5 mol% Cu(Ac) 2 1 atm 2, 27 C, 6h B() 2 () 88% 12% EP spectroscopy shows catalyst resting state as Cu II no strong field aryl ligand evident consistent with transmetalation being as turnover-limiting reaction progress correlated with EP spectra King, A. E.; Brunold, T. C.; Stahl. S. S. J. Am. Chem. Soc. 2009, 131,
44 Chan-Evans-Lam Coupling equilibrium prior to transmetalation B 5 mol% Cu(Ac) 2 1 atm 2, 27 C, 6h B() 2 () 88% 12% King, A. E.; yland, B. L.; Brunold, T. C.; Stahl, S. S. rganometallics, 2012, 31, 7948.
45 Chan-Evans-Lam Coupling equilibrium prior to transmetalation B 5 mol% Cu(Ac) 2 1 atm 2, 27 C, 6h B() 2 () 88% 12% deviation from standard conditions effect on efficiency added acetate inhibition added acetic acid inhibition Cu(Cl 4 ) 2 instead of Cu(Ac) 2 no reactivity King, A. E.; yland, B. L.; Brunold, T. C.; Stahl, S. S. rganometallics, 2012, 31, 7948.
46 Chan-Evans-Lam Coupling equilibrium prior to transmetalation B 5 mol% Cu(Ac) 2 1 atm 2, 27 C, 6h B() 2 () 88% 12% deviation from standard conditions effect on efficiency added acetate inhibition added acetic acid inhibition Cu(Cl 4 ) 2 instead of Cu(Ac) 2 no reactivity Cu(Cl 4 ) equiv aac rate acceleration Cu(Cl 4 ) equiv a rate acceleration King, A. E.; yland, B. L.; Brunold, T. C.; Stahl, S. S. rganometallics, 2012, 31, 7948.
47 Chan-Evans-Lam Coupling EP spectroscopy King, A. E.; yland, B. L.; Brunold, T. C.; Stahl, S. S. rganometallics, 2012, 31, 7948.
48 Chan-Evans-Lam Coupling EP spectroscopy EP signals appears after addition of boronic ester King, A. E.; yland, B. L.; Brunold, T. C.; Stahl, S. S. rganometallics, 2012, 31, 7948.
49 Chan-Evans-Lam Coupling EP spectroscopy EP signals appears after addition of boronic ester exhibits a saturation depedence on concentration of ester King, A. E.; yland, B. L.; Brunold, T. C.; Stahl, S. S. rganometallics, 2012, 31, 7948.
50 Chan-Evans-Lam Coupling EP spectroscopy acetic acid additive sodium acetate additive both display an inhibitory effect on EP signal suggesting that paddlewheel structure is stabilized King, A. E.; yland, B. L.; Brunold, T. C.; Stahl, S. S. rganometallics, 2012, 31, 7948.
51 Chan-Evans-Lam Coupling EP spectroscopy EP signal obtained immediately after mixing Cu(Ac) 2 and boronic ester displays two species King, A. E.; yland, B. L.; Brunold, T. C.; Stahl, S. S. rganometallics, 2012, 31, 7948.
52 Chan-Evans-Lam Coupling EP spectroscopy EP signal obtained immediately after mixing Cu(Ac) 2 and boronic ester displays two species relative concentrations of the two species are altered by the addition of additives King, A. E.; yland, B. L.; Brunold, T. C.; Stahl, S. S. rganometallics, 2012, 31, 7948.
53 Chan-Evans-Lam Coupling mechanism of transmetalation B 1/2[Cu(Ac) 2 ] 2 Cu II (Ac) B Ac Cu II B inhibitory effect of added acetate King, A. E.; yland, B. L.; Brunold, T. C.; Stahl, S. S. rganometallics, 2012, 31, 7948.
![Chan-Evans-Lam Coupling mechanism of transmetalation B 1/2[Cu(Ac) 2 ] 2 Cu II (Ac) B Ac Cu II B Cu II B Cu II B Ac](/docs-images/81/82959845/images/54-0.jpg "inhibitory effect of added acetic acid King, A. E.; yland, B. L.; Brunold, T. C.; Stahl, S. S. rganometallics, 2012, 31, 7948.")
54 Chan-Evans-Lam Coupling mechanism of transmetalation B 1/2[Cu(Ac) 2 ] 2 Cu II (Ac) B Ac Cu II B Cu II B Cu II B Ac inhibitory effect of added acetic acid King, A. E.; yland, B. L.; Brunold, T. C.; Stahl, S. S. rganometallics, 2012, 31, 7948.
55 Chan-Evans-Lam Coupling mechanism of transmetalation B 1/2[Cu(Ac) 2 ] 2 Cu II (Ac) B Ac Cu II B Cu II B Cu II B irreversible transmetalation Cu II Ac inhibitory effect of added acetic acid B aryl Cu(II) King, A. E.; yland, B. L.; Brunold, T. C.; Stahl, S. S. rganometallics, 2012, 31, 7948.
56 Chan-Evans-Lam Coupling mechanism of oxidative coupling Cu(II) nucleophile coordination lowerscu II /Cu III redox potential Cu(II) Copper xidase mechanism King, A. E.; yland, B. L.; Brunold, T. C.; Stahl, S. S. rganometallics, 2012, 31, 7948.
57 Chan-Evans-Lam Coupling mechanism of oxidative coupling Cu(II) B irreversible and turnover-limiting transmetalation nucleophile coordination lowerscu II /Cu III redox potential Cu(II) Cu(II) Copper xidase mechanism King, A. E.; yland, B. L.; Brunold, T. C.; Stahl, S. S. rganometallics, 2012, 31, 7948.
58 Chan-Evans-Lam Coupling mechanism of oxidative coupling Cu(II) B irreversible and turnover-limiting transmetalation nucleophile coordination lowerscu II /Cu III redox potential Cu(II) Cu(II) Copper xidase mechanism Cu(II) Cu(III) Cu(I) xidation to Cu(III) stoichiometry determined from single turnover experiment King, A. E.; yland, B. L.; Brunold, T. C.; Stahl, S. S. rganometallics, 2012, 31, 7948.
59 Chan-Evans-Lam Coupling mechanism of oxidative coupling Cu(II) B irreversible and turnover-limiting transmetalation nucleophile coordination lowerscu II /Cu III redox potential Cu(II) Cu(II) Copper xidase mechanism Cu(I) Cu(II) reductive elimination Cu(III) Cu(I) xidation to Cu(III) stoichiometry determined from single turnover experiment King, A. E.; yland, B. L.; Brunold, T. C.; Stahl, S. S. rganometallics, 2012, 31, 7948.
60 Chan-Evans-Lam Coupling mechanism of oxidative coupling Cu(II) B irreversible and turnover-limiting transmetalation nucleophile coordination lowerscu II /Cu III redox potential Cu(II) Cu(II) 2 Copper xidase stoichiometry determined from single turnover experiment 2 Cu(I) mechanism Cu(II) reductive elimination Cu(III) Cu(I) xidation to Cu(III) stoichiometry determined from single turnover experiment King, A. E.; yland, B. L.; Brunold, T. C.; Stahl, S. S. rganometallics, 2012, 31, 7948.
61 Copper in Cross-Coupling eactions B u =,, S = halide nucleophile = halide oxidative coupling standard cross-coupling oxidative coupling u Chan-Evans-Lam Ullmann-Goldberg "Aromatic Glaser-ay"
62 Ullmann-Goldberg eaction cross-coupling reaction mediated by Cu I /Cu III redox cycle Classic Ullmann-Goldberg reaction 2 equiv. Cu I L 2 equiv. = Br, Cl, I symmetric biaryl bond
63 Ullmann-Goldberg eaction cross-coupling reaction mediated by Cu I /Cu III redox cycle Classic Ullmann-Goldberg reaction 2 equiv. Cu I L 2 equiv. = Br, Cl, I symmetric biaryl bond Ullmann-type coupling u Cu I L u = Br, Cl, I C heteroatom bond
64 Ullmann-Goldberg eaction cross-coupling reaction mediated by Cu I /Cu III redox cycle nucleophile coordination/ deprotonation Cu I Cu I proposed mechanism
65 Ullmann-Goldberg eaction cross-coupling reaction mediated by Cu I /Cu III redox cycle nucleophile coordination/ deprotonation 1 2 Cu I reversible oxidative addition 1 2 proposed mechanism Cu I 1 CuIII 2
66 Ullmann-Goldberg eaction cross-coupling reaction mediated by Cu I /Cu III redox cycle nucleophile coordination/ deprotonation 1 2 Cu I reversible oxidative addition 1 2 proposed mechanism Cu I 1 CuIII 2 reductive elimination 1 2
67 Ullmann-Goldberg eaction cross-coupling reaction mediated by Cu I /Cu III redox cycle 1 2 CuIII putative aryl Cu III Cu III has been widely proposed as an intermediate oxidative addition product has never been observed oxidative addition to Cu has no precedent
68 Ullmann-Goldberg eaction cross-coupling reaction mediated by Cu I /Cu III redox cycle 1 2 CuIII putative aryl Cu III utilization of constraining macrocyclic ligands UV-Vis spectroscopy (M, CV, -ray) kinetics
69 Ullmann-Goldberg eaction kinetics reveal reversible oxidative addition 2 CuTf, aq Br acetone 2 Cohen, T.; Cristea, I. J. Am. Chem. Soc. 1976, 98,
70 Ullmann-Goldberg eaction kinetics reveal reversible oxidative addition 2 CuTf, aq Br acetone 2 formation of 2, 2'-dinitro-biphenyl: formation of nitrobenzene: 2 CuTf 2 CuTf Br Br 2 nd order dependence 1 st order 1 st order 1 st order Cohen, T.; Cristea, I. J. Am. Chem. Soc. 1976, 98,
71 Ullmann-Goldberg eaction kinetics reveal reversible oxidative addition 2 CuTf, aq Br acetone 2 2 k 1 2 Cu Tf Cu III Br Br k Cu III Br k 2 2 Br 2 Cohen, T.; Cristea, I. J. Am. Chem. Soc. 1976, 98,
72 Ullmann-type Coupling eaction direction observation of Cu I /Cu III redox steps ibas and Stahl's strategy: x Cu Cu III Cu I macrocyclic ligand shown to undergo C insertion with Cu highly constrained and stabilized aryl Cu III species Casitas, A.; King, A. E.; Parella, T.; Costas, M.; Stahl, S. S.; ibas,. Chem Sci. 2010, 1,
73 Ullmann-type Coupling eaction direction observation of Cu I /Cu III redox steps ibas and Stahl's strategy: x Cu Cu III Cu I macrocyclic ligand shown to undergo C insertion with Cu highly constrained and stabilized aryl Cu III species allows for characterization by 1 M, CV and UV-Vis allows for study of reductive elmination Casitas, A.; King, A. E.; Parella, T.; Costas, M.; Stahl, S. S.; ibas,. Chem Sci. 2010, 1,
74 Ullmann-type Coupling eaction direction observation of Cu I /Cu III redox steps ibas and Stahl's strategy: Cu I Cu III x Casitas, A.; King, A. E.; Parella, T.; Costas, M.; Stahl, S. S.; ibas,. Chem Sci. 2010, 1,
75 Ullmann-type Coupling eaction direction observation of Cu I /Cu III redox steps ibas and Stahl's strategy: Cu I Cu III x allows for study of oxidative addition allows for study of mechanism of C bond formation Casitas, A.; King, A. E.; Parella, T.; Costas, M.; Stahl, S. S.; ibas,. Chem Sci. 2010, 1,
76 Ullmann-type Coupling eaction characterization of aryl-cu III complex CuCl 2 or CuBr 2 Cu III x CuCl or CuBr Casitas, A.; King, A. E.; Parella, T.; Costas, M.; Stahl, S. S.; ibas,. Chem Sci. 2010, 1,
77 Ullmann-type Coupling eaction characterization of aryl-cu III complex CuCl 2 or CuBr 2 Cu III x CuCl or CuBr Casitas, A.; King, A. E.; Parella, T.; Costas, M.; Stahl, S. S.; ibas,. Chem Sci. 2010, 1,
78 Ullmann-type Coupling eaction characterization of aryl-cu III complex CuCl 2 or CuBr 2 Cu III x CuCl or CuBr electronic spectra (LMCT): agrees with ligand field strengths of the halides 369 and 521 nm 399 and 550 nm 422 and 635 nm Casitas, A.; King, A. E.; Parella, T.; Costas, M.; Stahl, S. S.; ibas,. Chem Sci. 2010, 1,
79 Ullmann-type Coupling eaction characterization of aryl-cu III complex CuCl 2 or CuBr 2 Cu III x CuCl or CuBr cyclic voltammetry: values for Cu III /Cu II redox couple 330mV 310mV 300mV Casitas, A.; King, A. E.; Parella, T.; Costas, M.; Stahl, S. S.; ibas,. Chem Sci. 2010, 1,
80 Ullmann-type Coupling eaction reductive elimination CuCl 2 Cu III x Tf ( equiv) C, 298K <1hr Cl quantitative Casitas, A.; King, A. E.; Parella, T.; Costas, M.; Stahl, S. S.; ibas,. Chem Sci. 2010, 1,
81 Ullmann-type Coupling eaction reductive elimination CuCl 2 Cu III x Tf ( equiv) C, 298K <1hr Cl quantitative Casitas, A.; King, A. E.; Parella, T.; Costas, M.; Stahl, S. S.; ibas,. Chem Sci. 2010, 1,
82 Ullmann-type Coupling eaction reductive elimination CuCl 2 Cu III x Tf ( equiv) C, 298K <1hr Cl quantitative E 1/2 (mv) k obs (S 1 ) (298K) complex x Cl (6)x10-2 Cu III Br Cl (5)x (5)x10-3 rate of reductive elimination controlled by C halogen bond strength C reductive elimination rates do not correlate with E 1/2 values Casitas, A.; King, A. E.; Parella, T.; Costas, M.; Stahl, S. S.; ibas,. Chem Sci. 2010, 1,
83 Ullmann-type Coupling eaction reductive elimination -pyr Cu III Br Br Br 3.3 mol% Cu(C) 4 PF 6 CD 3 C, 298K -pyr Casitas, A.; King, A. E.; Parella, T.; Costas, M.; Stahl, S. S.; ibas,. Chem Sci. 2010, 1,
84 Ullmann-type Coupling eaction relationship of this study to the Ullmann reaction Br 3.3 mol% Cu(C) 4 PF 6 CD 3 C, 298K -pyr 2 Cu I Cu I /Cu III Cu I 2 3 Cu III Casitas, A.; King, A. E.; Parella, T.; Costas, M.; Stahl, S. S.; ibas,. Chem Sci. 2010, 1,
85 Ullmann-type Coupling eaction relationship of this study to the Ullmann reaction Br 3.3 mol% Cu(C) 4 PF 6 CD 3 C, 298K -pyr 2 Cu I macrocyclic ligand lowers barrier to oxidative addition macrocyclic ligand stabilizes Cu III Cu I /Cu III *effectively inverts the relative rates of both redox steps Cu I 2 3 Cu III Casitas, A.; King, A. E.; Parella, T.; Costas, M.; Stahl, S. S.; ibas,. Chem Sci. 2010, 1,
86 Ullmann-type Coupling eaction relationship of this study to the Ullmann reaction Br 3.3 mol% Cu(C) 4 PF 6 CD 3 C, 298K -pyr 2 Cu I macrocyclic ligand lowers barrier to oxidative addition macrocyclic ligand stabilizes Cu III Cu I /Cu III *effectively inverts the relative rates of both redox steps Cu I 2 3 Cu III 1 mechanism of Ullmann-Goldberg can vary *use of less coordinating nucleophiles or higher coordinate ligands can affect key redox steps Casitas, A.; King, A. E.; Parella, T.; Costas, M.; Stahl, S. S.; ibas,. Chem Sci. 2010, 1,
87 Copper in Cross-Coupling eactions B u =,, S = halide nucleophile = halide oxidative coupling standard cross-coupling oxidative coupling u Chan-Evans-Lam Ullmann-Goldberg "Aromatic Glaser-ay"
88 Glaser-ay Type Couplings oxidative cross-coupling xidative coupling of a Cu-bound nucleophile and a C bond Cu 2 2 Z 2 Z amada, T; Ye,.; Stahl, S. S. J. Am. Chem. Soc. 2008, 130,
89 Glaser-ay Type Couplings oxidative cross-coupling xidative coupling of a Cu-bound nucleophile and a C bond Cu 2 2 Z 2 Z Cu II Cu III Cu I amada, T; Ye,.; Stahl, S. S. J. Am. Chem. Soc. 2008, 130, Brasche, G.; Buchwald, S. L. Angew. Chem. Int. Ed. 2008, 47, Yang, L.; Lu, Z.; Stahl, S. S. Chem Commun, 2009,
90 Glaser-ay Type Couplings oxidative cross-coupling xidative coupling of a Cu-bound nucleophile and a C bond Cu 2 2 Z 2 Z Ar Cu 2 Ar =, Li Cu = Cl, Br 2 amada, T; Ye,.; Stahl, S. S. J. Am. Chem. Soc. 2008, 130, Brasche, G.; Buchwald, S. L. Angew. Chem. Int. Ed. 2008, 47, Yang, L.; Lu, Z.; Stahl, S. S. Chem Commun, 2009,
91 Glaser-ay Type Couplings oxidative cross-coupling xidative coupling of a Cu-bound nucleophile and a C bond Cu 2 2 Z 2 Z Ar Cu 2 Ar =, Li Cu = Cl, Br 2 amada, T; Ye,.; Stahl, S. S. J. Am. Chem. Soc. 2008, 130, Brasche, G.; Buchwald, S. L. Angew. Chem. Int. Ed. 2008, 47, Yang, L.; Lu, Z.; Stahl, S. S. Chem Commun, 2009,
92 Glaser-ay Type Couplings oxidative cross-coupling Li = Cl, Br Cu 2 2 equiv. Cu 2 Ac Yang, L.; Lu, Z.; Stahl, S. S. Chem Commun, 2009,
93 Glaser-ay Type Couplings oxidative cross-coupling Li = Cl, Br Cu 2 2 equiv. Cu 2 Ac Cu(Ac) 2 Cu(Tf) 2 Cu(Cl 4 ) 2 CuF 2 CuCl 2 CuBr 2 Yang, L.; Lu, Z.; Stahl, S. S. Chem Commun, 2009,
94 Glaser-ay Type Couplings oxidative cross-coupling Li = Cl, Br Cu 2 2 equiv. Cu 2 Cl Cl Ac Cl Cu(Ac) 2 70% 7% Cu(Tf) 2 Cu(Cl 4 ) 2 CuF 2 CuCl 2 CuBr 2 Yang, L.; Lu, Z.; Stahl, S. S. Chem Commun, 2009,
95 Glaser-ay Type Couplings preliminary investigations Li = Cl, Br Cu 2 LiBr 25 mol% CuBr 2 Br Ac, 60 C Yang, L.; Lu, Z.; Stahl, S. S. Chem Commun, 2009,
96 Glaser-ay Type Couplings preliminary investigations Li = Cl, Br Cu 2 LiBr 25 mol% CuBr 2 Br Ac, 60 C LiCl 25 mol% CuCl 2 Cl 6 equiv. Ac, 100 C Yang, L.; Lu, Z.; Stahl, S. S. Chem Commun, 2009,
97 Glaser-ay Type Couplings preliminary investigations Li = Cl, Br Cu 2 LiBr 25 mol% CuBr 2 Br Ac, 60 C Δ CuBr 2 2 CuBr Br 2 regioselectivity follows that of electrophilic aromatic bromination Barnes, J. C.; ume, D.. Inorg. Chem. 1963, 2, Yang, L.; Lu, Z.; Stahl, S. S. Chem Commun, 2009,
98 Glaser-ay Type Couplings preliminary investigations Li = Cl, Br Cu 2 20 mol% a equiv Br Br Δ CuBr 2 2 CuBr Br 2 regioselectivity follows that of electrophilic aromatic bromination Zhang, G.; Liu,.; u, Q.; Ma, L.; Liang,. Adv. Synth. Catal. 2006, 346, Barnes, J. C.; ume, D.. Inorg. Chem. 1963, 2, Yang, L.; Lu, Z.; Stahl, S. S. Chem Commun, 2009,
99 Glaser-ay Type Couplings preliminary investigations Li = Cl, Br Cu 2 25 mol% CuBr 2 Br Ac, 2, LiBr Br 75% Δ CuBr 2 2 CuBr Br 2 regioselectivity follows that of electrophilic aromatic bromination Zhang, G.; Liu,.; u, Q.; Ma, L.; Liang,. Adv. Synth. Catal. 2006, 346, Barnes, J. C.; ume, D.. Inorg. Chem. 1963, 2, Yang, L.; Lu, Z.; Stahl, S. S. Chem Commun, 2009,
100 Glaser-ay Type Couplings oxidative cross-coupling xidative coupling of a Cu-bound nucleophile and a C bond Cu 2 2 Z 2 Z Ar Cu 2 Ar =, Li Cu = Cl, Br 2 amada, T; Ye,.; Stahl, S. S. J. Am. Chem. Soc. 2008, 130, Brasche, G.; Buchwald, S. L. Angew. Chem. Int. Ed. 2008, 47, Yang, L.; Lu, Z.; Stahl, S. S. Chem Commun, 2009,
101 Glaser-ay Type Couplings oxidative cross-coupling xidative coupling of a Cu-bound nucleophile and a C bond Cu 2 2 Z 2 Z Ar Cu 2 Ar =, Li Cu = Cl, Br 2 amada, T; Ye,.; Stahl, S. S. J. Am. Chem. Soc. 2008, 130, Brasche, G.; Buchwald, S. L. Angew. Chem. Int. Ed. 2008, 47, Yang, L.; Lu, Z.; Stahl, S. S. Chem Commun, 2009,
102 Glaser-ay Type Couplings evidence for an aryl-cu III King, A. E.; uffman, L. M.; Casitas, A.; Costas, M.; ibas,.; Stahl, S. S. J. Am Chem. Soc, 2010,
103 Glaser-ay Type Couplings evidence for an aryl-cu III CuBr 2 Br C Cu III Br Cu I King, A. E.; uffman, L. M.; Casitas, A.; Costas, M.; ibas,.; Stahl, S. S. J. Am Chem. Soc, 2010,
104 Glaser-ay Type Couplings evidence for an aryl-cu III CuBr 2 Br C Cu III Br Cu I Cu III Br C King, A. E.; uffman, L. M.; Casitas, A.; Costas, M.; ibas,.; Stahl, S. S. J. Am Chem. Soc, 2010,
105 Glaser-ay Type Couplings evidence for an aryl-cu III CuBr 2 Br C Cu III Br Cu I Cu III Br C Br Cu III C pyr King, A. E.; uffman, L. M.; Casitas, A.; Costas, M.; ibas,.; Stahl, S. S. J. Am Chem. Soc, 2010,
106 Glaser-ay Type Couplings kinetics of methoxylation reaction using the method of intial rates Cu III Br C kinetics determined by 2 consumption King, A. E.; uffman, L. M.; Casitas, A.; Costas, M.; ibas,.; Stahl, S. S. J. Am Chem. Soc, 2010,
107 Glaser-ay Type Couplings kinetics of methoxylation reaction using the method of intial rates Cu III Br C arene ligand (mm) Cu II (mm) p 2 (torr) 1 st order dependence 1 st order dependence 0 order dependence King, A. E.; uffman, L. M.; Casitas, A.; Costas, M.; ibas,.; Stahl, S. S. J. Am Chem. Soc, 2010,
108 Glaser-ay Type Couplings kinetics of methoxylation reaction using the method of intial rates Cu III Br C arene ligand (mm) Cu II (mm) p 2 (torr) 1 st order dependence 1 st order dependence 0 order dependence catalytic steps involving 2 are comparatively fast Cu reoxidation is not rate-determining King, A. E.; uffman, L. M.; Casitas, A.; Costas, M.; ibas,.; Stahl, S. S. J. Am Chem. Soc, 2010,
109 Glaser-ay Type Couplings kinetics of methoxylation reaction using the method of intial rates Cu III Br C 1 M complicated due to paramagnetic line broadening indicates that Cu II is formed during reaction King, A. E.; uffman, L. M.; Casitas, A.; Costas, M.; ibas,.; Stahl, S. S. J. Am Chem. Soc, 2010,
110 Glaser-ay Type Couplings kinetics of methoxylation reaction using the method of intial rates Cu III Br C Cu III Cu II King, A. E.; uffman, L. M.; Casitas, A.; Costas, M.; ibas,.; Stahl, S. S. J. Am Chem. Soc, 2010,
111 Glaser-ay Type Couplings kinetics of methoxylation reaction using the method of intial rates Cu III Br C Cu III Cu II King, A. E.; uffman, L. M.; Casitas, A.; Costas, M.; ibas,.; Stahl, S. S. J. Am Chem. Soc, 2010,
112 Glaser-ay Type Couplings proposed mechanism of Aromatic Glaser-ay coupling Cu II Cu II King, A. E.; uffman, L. M.; Casitas, A.; Costas, M.; ibas,.; Stahl, S. S. J. Am Chem. Soc, 2010,
113 Glaser-ay Type Couplings proposed mechanism of Aromatic Glaser-ay coupling Cu II Cu I Br Cu II Cu III King, A. E.; uffman, L. M.; Casitas, A.; Costas, M.; ibas,.; Stahl, S. S. J. Am Chem. Soc, 2010,
114 Glaser-ay Type Couplings proposed mechanism of Aromatic Glaser-ay coupling Cu II Cu I Br Cu II Cu III 2 2 Cu I King, A. E.; uffman, L. M.; Casitas, A.; Costas, M.; ibas,.; Stahl, S. S. J. Am Chem. Soc, 2010,
115 Glaser-ay Type Couplings proposed mechanism of Aromatic Glaser-ay coupling Cu II Cu I Br accounts for apparent build-up of Cu II during reaction Cu II Cu III 2 2 Cu I King, A. E.; uffman, L. M.; Casitas, A.; Costas, M.; ibas,.; Stahl, S. S. J. Am Chem. Soc, 2010,
116 Copper in Cross-Coupling eactions B u =,, S = halide nucleophile = halide oxidative coupling standard cross-coupling oxidative coupling u Chan-Evans-Lam Ullmann-Goldberg "Aromatic Glaser-ay"
117 Copper in Cross-Coupling eactions
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