SUPPORTING INFORMATION

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Egbert Earl Hopkins
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1 SUPPORTING INFORMATION Cooperative Phosphine and Titanocene Catalysis: Accelerated C X Activation for Efficient Generation of Reactive Organometallics Lauren M. Fleury, Andrew D. Kosal, James T. Masters, and Brandon L. Ashfeld* Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN Contents 1. General S-2 2. Determination of stereoselectivity in the intramolecular allylations S-3 3. NMR spectra of new compounds S-4 S-1

2 1. General Solvents and reagents were reagent grade and used without purification unless otherwise noted. Tetrahydrofuran (THF) was passed through a column of molecular sieves and stored under argon. Benzaldehyde and p-anisaldehyde were distilled under vacuum over molecular sieves and stored under nitrogen. All other aldehydes and ketones were obtained from commercial sources and used without further purification unless a synthesis is forthwith described. Zn (0) dust was rinsed with 1M HCl, filtered and washed thoroughly with water, acetone and diethyl ether and dried under vacuum. All reactions were carried out in oven-dried glassware under nitrogen unless otherwise specified. Triphenylphosphine (PPh 3 ), tricyclohexylphosphine (PCy 3 ), diphenylphosphinoethane (dppe), diphenylphosphinopropane (dppp), diphenylphosphinobutane (dppb), diphenylphosphinoferrocene (dppf) and 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (rac-binap) were obtained through commercial sources and used without further purification. Ligands L1, L2, L3, L4, L5, L6, L7, L8 and L9 for asymmetric allylation were obtained from commercial sources taking any precautions for storage and handling as noted by manufacturer. 1 H nuclear magnetic resonance (NMR) spectra were obtained at either 300, 400, 500 or 600 MHz. 13 C NMR were obtained at 100, 125 or 150 MHz. Chemical shifts are reported in parts per million (ppm, δ), and referenced from the solvent or tetramethylsilane (TMS). Coupling constants are reported in Hertz (Hz). Spectral splitting patterns are designated as s, singlet; d, doublet; t, triplet; q, quartet; m, multiplet; comp, complex; app, apparent; and br, broad. Infrared (IR) spectra were obtained using a silicon (Si) crystal in an attenuated total reflectance (ATR) tower and reported as wavenumbers (cm -1 ). High and Low resolution fast atom bombardment (FAB) or electrospray ionization (ESI) measurements were made utilizing Time of Flight (TOF) mass analyzers. Analytical thin layer chromatography (TLC) was performed using 250 micron 60 F 254 silica gel plates, visualized with UV light and stained with either p-anisaldehyde, ceric ammonium nitrate or potassium permanganate solutions. Flash column chromatography was performed according to Still s procedure (Still, W. C.; Kahn, M.; Mitra, A. J. Org. Chem. 1978, 43, 2923) using EMD µm 60Å silica gel. S-2

3 2. Determination of stereoselectivity in the intramolecular allylations: 1 H NMR and 13 C NMR spectral data of 15a was consistent with literature reported values. 1 1 H NMR and 13 C NMR spectral data for 13a does not match literature known values for the antidiastereomer leading to determination of syn stereochemistry. Below are observed noes marked with arrows for 13a in comparision to literature values for anti-diastereomer of 13a and closely related synand anti-compound. 2,3 4.8% MeO 2 C CO 2 Me MeO 2 C CO 2 Me OH H H 8.5% OH H H 0.24% OH H H 6.5% (C 6 D 6 ) OH H H 1.7% (C 6 D 6 ) 13a anti diastereomer syn anti The relative stereochemistry of compounds 13b, 13c, c-13c, and 15b was tentatively assigned based on the structure of allylic alcohols 13a and 15a. Utilizing 1D noe 1 H NMR spectroscopy, we observed the key noes marked with arrows. The syn-assignment is consistant with closely related structures of previously reported metal calatyzed allylations. 2,4,5,6 MeO 2 C CO 2 Me H H OH H 14.4% 13b MeO 2 C CO 2 Me H HO CH 3 4% 13c O O CO 2 Me H 2% 8.2% H H CH 3 c-13c 8.2% 2% HO Ts N H 8.3% 3.2% 15b Chang, M.; Lin, C.; Pai, C. Tetrahedron Lett. 2006, 47, Loughlin, W. A.; Murphy, M. E.; Elson, K. E.; Henderson, L. C. Aust. J. Chem. 2004, 57, Paquette, L. A.; Mendez-Andion, J. L. J. Org. Chem. 1998, 63, Millan, A.; Campana, A. G.; Bazdi, B.; Miguel, D.; Alvarez De Cienfuegos, L.; Cuerva, J. M.; Echavarren, A. M. Chem. Eur. J., 2011, 17, Estevez, R. E.; Justicia, J.; Bazdi, B.; Fuentes, N.; Paradas, M.; Choquesillo-Lazarte, D.; Garcı a-ruiz, J. M.; Robles, R.; Gansauer, A.; Cuerva, J. M.; Oltra, J. E. Chem. Eur. J. 2009, 15, Campana, A. G.; Bazdi, B.; Fuentes, N.; Robles, R.; Cuerva, J. M.; Oltra, J. E.; Porcel, S.; Echavarren, A. M. Angew. Chem., Int. Ed. 2008, 46, S-3

Supporting Information

Supporting Information Titanocene-Catalyzed Conjugate Reduction of α,β -Unsaturated Carbonyl Derivatives Andrew D. Kosal and Brandon L. Ashfeld* Department of Chemistry and Biochemistry, University of