well over 100 groups worldwide are working on homogeneous gold-catalyzed reactions
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1 2010 Gold() prefers P or C ligands and a linear coordination geometry well over 100 groups worldwide are working on homogeneous gold-catalyzed reactions Catalysts Methodology Mechanisms ynthesis P KTP (tht) C 2 2,30min,rt P =, 99% = Me, quant AgTf 2 C 2 2,1h,rt Tf2 P =, 90% = Me, 87% to, awamura, ayashi 1986 A.. K. ashmi, L. chwarz, J.-. Choi, T. M. Frost, Angew. Chem. nt. d. ngl. 2000, 39, Up to 2000 turnovers (0.05 mol% of catalyst) > 350 citations to 1986 A.. K. ashmi, Chem. ev. 2007, 107, A.. K. ashmi, G. J. utchings, Angew. Chem. 2006, 45, A.. K. ashmi, Gold Bull. 2004, 37, aubenheimer 2002 A.. K. ashmi, A. Loos, A. Littmann,. Braun, J. Knight,. herty, F. ominger, Adv. ynth. Catal. 2009, 351, Gold() prefers P or C ligands and a linear coordination geometry Gold() prefers or and a square-planar coordination geometry TT 1 C DCM, T 1 C 3 2 DCM, T Up to 3000 turnovers with a problematic substrate aubenheimer 2002 errmann 2003 A.. K. ashmi, T. engst, C. Lothschütz, F. ominger, Adv. ynth. Catal. 2010, 352, Utimoto 1987 A.. K. ashmi, J. P. Weyrauch, M. udolph,. Kurpejovic, Angew. Chem. nt. d. 2004, 43,
2 Frontier rbitals of 3? What is the General eactivity Pattern? u u u LUM u u u M B3LP with tuttgart CP and basis for and 6-31G(d,p) on other atoms David Willock, Cardiff u - L - L - L u u Modification of the eactivity Pattern u u u Cyclisation in the presence of water u u u u u u u
3 ubstituents = 5-exo-dig () 2 = 6-endo-dig () 1 table vinylgold P AgTf 2 3 P intermediates t Toluene 1 L.-P. Liu, B. u, M.. Mashuta, G. B. ammond, J. Am. Chem. oc. 2008, 130, Me Me 2 C C 2 Me Me 3 P - Me Me 2 C C 2 Me Me P 3 D. Weber, M. A. Tarselli, M.. Gagné, Angew. Chem. 2009, 121, ; Angew. Chem. nt. d. 2009, 48, (Pr) 1 2 (Pr) (Pr) (Pr) 1 2 (Pr) (Pr) 1 2 ubstituents table organogold intermdiates of other reactions (Pr) t 3 TF, T (Pr) (42%) 2.038(6), 2.027(5) enyl, Methyl 63% Adamantyl, Methyl 58% Adamantyl, Butyl 71% 2,5-Dimethylfur-3-yl, Methyl 62% A.. K. ashmi, A. chuster, F. ominger, Angew. Chem. nt. d. 2009, 48, (Pr) t 3 TF, T (Pr) (60%) A.. K. ashmi, T. D. amamurthi, F. ominger, Adv. ynth. Catal. 2010, 352,
4 ? ther lectrophiles? A. Buzas, F. Gagosz, rg. Lett. 2006, 8, A. Buzas, F. Gagosz, ynlett 2006, ; A. Buzas, F. strate, F. Gagosz, rg. Lett. 2006, 8, F. Kirsch, Angew. Chem. nt. d. 2007, 46, L. Zhang, rg. Lett. 2007, 9, B. Crone,. F. Kirsch, J. rg. Chem. 2007, 72, K. Bhargava, F. Mohr, M. A. Bennett, L. L. Welling, A. C. Willis, rganometallics 2000, 19, Z. hi, C. e, J. Am. Chem. oc. 2004, 126, P () -fluorobenzenesulfonimide () () 91% al J. P. Weyrauch, A.. K. ashmi, A. chuster, T. engst,. chetter, A. Littmann, M. udolph, M. amzic, J. Visus, F. ominger, W. Frey, J. W. Bats, Chem. ur. J. 2010, 16, A.. K. ashmi, T. D. amamurthi, F. ominger, J. rganomet. Chem. 2009, 694, 592 submitted on 17th ctober 2008 G. Zhang,. Peng, L. Cui, L. Zhang, Angew. Chem. nt. d. 2009, 48, 3112 submitted on 1st February 2009 P source of " " - 3 P L. Cui, G. Zhang, L. Zhang, Bioorg. Med. Chem. Lett. 2009, 19, 3884 submitted on 17th February 2009 () () = al, D 1 2 B() 2 electfluor 1 2 A.. K. ashmi, T. D. amamurthi, F. ominger, J. rganomet. Chem. 2009, 694, M.. opkinson, A. Tessier, A. alisbury, G. T. Giuffredi, L.. Combettes, A. D. Gee, V. Gouverneur, Chem. ur. J. 2010, 16, 4739 ( 1 ) -- ( 2 ) -- ox --> 1-2? The Future? [()] A - [()] M - M Pd() compound as the electrophile L! L 2 Pd() B L 2 Pd() - L 2 Pd 2 Me - L 2 Pd 0 Pd L 2 Me Pd L 2 ipr ipr L.-P. Liu, B. u, M.. Mashuta, G. B. ammond, J. Am. Chem. oc. 2008, 130, Me 3 P L 2 = dppf P 3 ipr ipr Me 3 P C 2 t - saves a C- activation - orthogonality of /Pd - adds another dimension to gold catalysis A.. K. ashmi, C. Lothschütz,. Döpp, M. udolph, T. D. amamurthi, F. ominger, Angew. Chem. nt. d. 2009, 48, examples A.. K. ashmi, C. Lothschütz,. Döpp, M. udolph, T. D. amamurthi, F. ominger, Angew. Chem. nt. d. 2009, 48,
5 3P [Pd 2(dppf)] MeC, 60 C 3P C 3P [Pd 2(dppf)] MeC, 60 C C 3P 2 77% C Br 91% C 39% Br 85% 2 83% 3P 91% 3P 88% 3P Bn 90% 73% 95% 84% 89% 78% 3 3P 3P 71% 92% 81% 73% 80% Me 2C 91% 91% 70% Br 87% 82% A.. K. ashmi,. Döpp, C. Lothschütz, M. udolph, D. iedel, F. ominger, Adv. ynth. Catal. 2010, 352, A.. K. ashmi,. Döpp, C. Lothschütz, M. udolph, D. iedel, F. ominger, Adv. ynth. Catal. 2010, 352, The Gold-Catalyzed enol ynthesis: The Mechanistic Picture Change of the eaction Pathway: a) nsertion of the Alkyne into the Furylic C-C Bond n B. Martín-Matute, D. J. Cardenas, A. M. chavarren, Angew. Chem. nt. d. 2001, 40, A.. K. ashmi, M. udolph, J. P. Weyrauch, M. Wölfle, W. Frey, J. W. Bats, Angew. Chem. nt. d. 2005, 44,
6 Change of the eaction Pathway: a) nsertion of the Alkyne into the Furylic C-C Bond Change of the eaction Pathway: a) nsertion of the Alkyne into the Furylic C-C Bond -cat Mechanism: Control xperiment 42% 78% Me 29% (d.r. 80:20) 47% * 2 5 mol% -cat CD 2 2 T * 2 44% 30% 20% 15 %ee 0 %ee 43% Me. chäfer,. Panjankastan, T. engst, A.. K. ashmi, unpublished results. T. engst, A.. K. ashmi, unpublished results. Change of the eaction Pathway: b) ydroarylation of the Furan Change of the eaction Pathway: b) ydroarylation of the Furan Me 3 i -cat. Me 3 i Me 3 i Me 3 i Me 3 i TBDM TBDM 84% TBDM 31% 37% A.. K. ashmi, P. aufe, C. chmid, A. ivas ass, W. Frey, Chem. ur. J. 2006, 12,
7 Change of the eaction Pathway: c) Polycyclic Compounds Change of the eaction Pathway: c) Polycyclic Compounds ynthesis of the ubstrates Z, =, ' Change of the eaction Pathway: c) Polycyclic Compounds Change of the eaction Pathway: c) Polycyclic Compounds -cat. Me 54% 97% 70% 75%, d.r. 90:10 52% 74% 83%, d.r. 71:29 A.. K. ashmi, M. udolph, J. uck, W. Frey, J. W. Bats, M. amzic, Angew. Chem. 2009, 48,
8 Change of the eaction Pathway: d) Polycyclic Compounds Change of the eaction Pathway: d) Polycyclic Compounds -cat. Me s 53% 65% Me 57% 75% 74% 53% 79% 60% Me 53% 72% 76% A.. K. ashmi,. Panjankastan, M. udolph, F. ominger, W. Frey, Adv. ynth. Catal. 2009, 351, % Change of the eaction Pathway: e) Polycyclic Compounds Change of the eaction Pathway: d) Polycyclic Compounds -cat. [] [] [] -[] Me 56% 52% 50% A.. K. ashmi,. Panjankastan, M. udolph, F. ominger, W. Frey, Adv. ynth. Catal. 2009, 351,
9 Change of the eaction Pathway: f) Polycyclic Compounds V: Comparison of and PG [] n =1 n [] n =2 PG ummary 1. Gold is not too expensive for catalysis 2. Activation for ucleophilic Attack 3. ighest eactivity 4. o Precautions, Water and Air Tolerated 5. o Paramagnetic pecies 6. sohypsic eactions 7. Fast Proto-Desauration A.. K. ashmi, Chemistry in stralia 2009, May, 7-10.
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