Homogeneous Gold Catalysis - Unique Reactivity for Activation of C C Multiple Bonds
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1 1 rganic Seminar omogeneous Gold Catalysis - Unique Reactivity for Activation of C C Multiple Bonds ysical rganic Chemistry Laboratory (Nakamura Laboratory) D2 Masaki Sekine
2 Development of Gold Catalysis 2 Gold is ighly stable. Dissolved only in aqua regia or such strong oxidants igh Price. Symbol of wealth. Money itself. Neglected in the field of organic chemistry for so long time. Number of publications on gold catalysis from 1900 to May Number of publications on homogeneous gold catalysis only omogeneous gold catalysis is still in the early stage. ashmi, A. S. K.; atchings, G. J. ACIE, 2006, 45, 7896.
3 Relativistic Effect in Gold 3 Relativistic contraction of the 6s shell Ionization potentials for the Group 11 and Group 12 transition metals Dirac-artree-Fock (DF): relativistic artree-fock (F): non-relativistic Pseudopotential (ps): without regard for f electrons Relativistic effects are crucial to understanding the electronic structure of gold (1) Pyykkö, P.; Desclaux, J. P. Acc. Chem. Res. 1979, 12, 276. (2) Pitzer, K. S. Chem. ys. Lett. 1975, 33,
4 Unique Reactivity of Gold(I) 4 Relativistic Effect Affects the Reactivity of Au(I) Comparison of Au and Ag bond energies Strong Lewis acidity Covalent-like bond with ligand share positive charge with ligand soft Lewis acid ighly and selectively activates soft electrophiles (π-systems) Pyykkö, P.; Desclaux, J. P. Acc. Chem. Res. 1979, 12, 276.
5 Initial Studies of Gold Catalysis (1) 5 Simplest Form of Nucleophilic Addition to a C C multiple bond [Au] + R' R R Nu Nu: [Au] ~ + R R' [Au] + Nu R' The Earliest Experiment: ydration of Alkynes 7 mol% [AuCl 4 ] R 1 R 2 R 1 Me/ 2, 65 ºC R 2 + [Au] Markovnikov addition ~ 38% (TN ~ 6) ~ + [Au] [Au] R 1 R R 1 [Au] 2 2 R 2 Thomas, C. B. et al. J. Chem. Soc. Perkin Trans. I, 1976, Gold(III) was recognized as a stoichiometric oxidant. cf.) Cu(II): Fehling solution Ag(I) : Tollens test The same reaction system was rediscovered in (Fukuda, Y.; Utimoto, K. J. rg. Chem. 1991, 56, 3729.)
6 Initial Studies of Gold Catalysis (2) 6 Superior Reactivity to ther Metal Cations ydroamination R 2 2 N R 1 5 mol% Na[AuCl 4 ] MeCN, rt, 12 h 6-exo-dig cyclization R 1 R 2 N R 2 N R 1 ~ quant. R Use of 5 mol% PdCl 2 (MeCN) 2 / EtCN / reflux / 20 h; 70% conversion. Asymmetric Aldol Reaction with Isocyanides Utimoto, K. et al. eterocycles 1987, 25, 297. CMe 1 mol% [Au(c-exNC) 2 ] + BF 4 R CMe R CMe Ligand + N N N C 2 Cl 2, rt, h ~ 100 % yield trans cis Ligand = Fe Me NMe(C 2 ) 2 NEt 2 P 2 igh enantioselectivity (> 90% ee) igh trans selectivity (> 97%) Use of Ag or Cu; low selectivity P 2 Ito, Y.; ayashi, T. JACS 1986, 108, 6406.
7 7 Difference of Reactivity between Au(I) and Au(III) Different xidation States Led to Divergent Product 2 mol% AuCl 3 2 mol% Et 3 PAuCl n-ct toluene n-ct toluene n-ct [Au(III)] n-ct [Au(III)] [Au(I)] [Au(I)] n-ct Gevorgyan, V. et al. JACS, 2005, 127, Theoretical Analysis (298 K, 1 atm) (B 3 LYP/LACV 3 P**//B 3 LYP/LACVP* level of theory)) G rel Cl 3 Au AuCl Au(III) thermodynamically prefers aldehyde coordination Straub, B. F. et al. Chem. Commun., 2004, 1726.
8 Ligand Effects on Au(I) Catalysis 8 Ac 2 mol% LAuCl / AgBF 4 + C Bu 2 Cl 2, rt, 5 min. Ac Bu Ac Bu entry ligand 2 (%) 3 (%) N N N N 1 P N N 2 ITM ITM IPr SIPr 3 4 SIPr IPr Bulky ligand prevent a direct hydroarylation step. Ac Bu 1 [Au + ] 1,3-shift [Au + ] Ac Bu 1,2-shift Bu 2 Ac Ac Ac [Au + ] 1,2-shift Ac 3 Bu Bu [Au] Bu Nolan, S. P. et al. ACIE 2006, 45, 3647.
9 Intramolecular Acetylenic Schmidt Reaction with a Diphosphine Ligand N mol% (dppm)(aucl) 2 5 mol% AgSbF 6 C 2 Cl 2, 35 ºC, 40 min. LAu N 84% N 9 LAu + N 2 N N 2 N N 2 Use of monodentate phosphine Recovery of SM LAu LAu Toste, F. D. et al. JACS 2005, 127, Possible Aurophilic Interaction R 2 P Au P 2 R inactive dppm 2 P Au ~ 3 Å, 7-12 kcal/mol. P Au 2 active catalyst Aurophilic interaction stabilizes the active monoligated catalyst? (still remains unclear.) (a) Schmidbaur,. et al. ACIEE, 1988, 27, (b) Toste, F. D. et al. ACIE 2010, 49, 5519.
10 Carbene Character of Au(I) Species 10 Au Calculated bond length: Non-relativistic: Å Relativistic: Å Au Calculated: Å Significant backbonding from Au(I) into vacant p orbitals on carbon Stabilize carbene intermediates Schwarz,. et al. JACS 1995, 117, 495. Barysz, M.; Pyykkö, P. Chem. ys. Lett. 1998, 285, 398. Comparison of Reactivities of Au(I) and In(III) InCl 3 (5 mol%) AuCl (5 mol%) [Au] [In] Fürstner, A. et al. Chem. Eur. J. 2004, 10, 4556.
11 Intramolecular Cycloisomerization of Enyne 11 Divergent Transformation of 1,6-Enynes (Echavarren, A. M. et al. Chem. Rev. 2008, 108, 3326.) LAu + R 1 Z R 2 R 3 R 4 5-exo-dig LAu R 1 Z R 2 R 3 R 4 Z = C(CMe) 2, NTs, C(S 2 ) 2, etc... 6-endo-dig Z AuL R 1 R 3 R 2 R 4
12 12 Mechanistic Insight of Cycloisomerization of Enyne 1-1 NESY Experiment on Equilibrium of Enyne-Au(I) π-complex Me 2 C [Au] Me 2 C A [Au] fast (at rt) Cycloisomerization Me 2 C Me 2 C [Au] A:B ~ 1:1 (at 223 K) [Au] Me 2 C Me 2 C! No preference in the coordination step to alkynes over alkenes B Bertrand, G. et al. PNAS 2007, 119, What Causes Selective Reaction Route? Energy levels of alkynesʼ LUMs are intrinsically lower than those of alkenesʼ (by ~0.5 ev) Alkenes are intrinsically more nucleophilic. Electrophilic alkynes become more electrophilic by Au(I) coordination.
13 Intermolecular [2+2] Cycloaddition 13 Difficulty of Intermolecular Cycloaddition Many possible products Resulting products could react further with the starting alkyne. Gold(I)-Catalyzed Intermolecular Cycloaddition for Cyclobutene Synthesis R 2 R 1 + R 4 R 3 t Bu [Au(I)] = [Au(I)] (3 mol%) C 2 Cl 2, rt, 7-72 h t Bu SbF P Au NCMe 6 i Pr i Pr i Pr R 1 R 4 R 3 R 2 20 examples 44-80% yield Bulky ligand prevents undesirable side-reaction. Echavarren, A. M. et al. JACS, 2010, 132, 9292.
14 Application for Total Synthesis 14 Total Synthesis of ( )-Englerins A (Echavarren, A. M. et al. ACIE, 2010, 49, 3517.) TES [IPrAu-NC]SbF 6 (3 mol%) C 2 Cl 2, rt, 5h TES Another synthetic route has been reported by K. C. Nicolau in 2010; 28 steps. 67% yield Single diastereomer ( )-Englerins A (inhibitor of renal cancer) 18 steps, 7% overall yield Enantioselective Tandem Reaction (Toste, F. D. et al. JACS 2010, 132, 8276.) Me Me Me Et 2 C Et 2 C 3 mol% Me-DTBM-BIPEP(AuCl) 2 3 mol% AgSbF 6 m-xylene, rt Et 2 C Et 2 C Me 61%, 97% ee 6 other similar examples
15 Gold Catalyzed Sonogashira Coupling? 15 I + [Au I ] cat. (20 mol%) K 3 P 4 (1.4 equiv) o-xylene, 130 ºC, 24 h 54% t Bu 3 P Au N Au P 3 N Au P 3 Au(I), which has the same d 10 electronic configuration as Pd metal and Cu(I), is active and very selective for performing the Sonogashira reaction. [Au I ] cat. Corma, A. et al. ACIE 2007, 46, Suspicious Points Au(I) is less nucleophilic metal species that do not tend to undergo oxidative addition. Even high-purity gold often contains traces of palladium. Nakamura, E. et al. JACS, 2005, 127, Agarwal, D. P. et al. Gold Bull. 1998, 31, 58.
16 Gold-Palladium Combination 16 Actually, Gold-Mediated Sonogashira Coupling with Palladium Ac + I AuI (2 mol%) dppe (2 mol%) K 2 C 3 [Pd] (x mol%) toluene, 130 ºC, 16 h Ac entry [Pd] a (mol%) conversion (%) yield (%) 1 < 2% < 2% a [Pd] = [Pd 2 (dba) 3 CCl 3 ] Without Palladium Alkynylation of [AuXL] occured easily. Reductive elimination from [AuAr(Alkynyl)XL] also occured very fast. xidative addition of ArX to [ArXL] or [Ar(Alkynyl)L] did not occur. Espinet, P.; Echavarren, A. M. et al. rg. Lett., 2010, 12, 3006.
17 Plausible Mechanism 17 Ac + I AuI (2 mol%) dppe (2 mol%) K 2 C 3 [Pd] (0.12 mol%) toluene, 130 ºC, 16 h Ac Au(I) works just as Cu(I) does. Espinet, P.; Echavarren, A. M. et al. rg. Lett., 2010, 12, 3006.
18 Summary 18 Gold is a soft transition metal and thus prefers other soft partners, such as carbon π-systems. Gold often reacts much faster and in milder condition than other transition metals. Selectivities are also very different due to the preference to the carbene-intermediates. In gold homogeneous catalysis, oxidative addition and β-hydride elimination scarcely occur, resulting in the difficulties of general crosscoupling reactions. Gold-catalyzed tandem reactions are to be one of the strongest strategies for the total syntheses of polycyclic compounds.
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