SI - 1 Supporting Information Total Synthesis of (–)-Callystatin A. Neil F. Langille and James S. Panek* Department of Chemistry and Center for Chemical Methodology and Library Development, Metcalf Center for Science and Engineering, Boston University, 590 Commonwealth Avenue, Boston, Massachusetts 02215 Experimental section: 1 H and 13 C NMR spectra were taken in CDCl 3 at 400 MHz and 75 MHz, respectively. Chemical shifts are reported in parts per million using the solvent internal standard (chloroform, 7.24 and 77.0 ppm, respectively). Data are reported as follows: chemical shift, integration, multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, br = broad, ABq = AB quartet), coupling constant. A dagger (†) denotes spectrum included at end of Supporting Information (p. 19-29). Diastereomeric ratios were determined by 1 H NMR (400 MHz) analysis of crude mixtures, operating at signal/noise ratio of >200/1. Infrared resonance spectra were recorded on a Nexus™ 670 FTIR spectrometer. High resolution mass spectra were obtained on a Finigan™ MAT-90 spectrometer. Optical rotations were recorded on an AUTOPOL III digital polarimeter at 589 nm. CH 2 Cl 2 , MeOH, PhMe, Et 2 O, PhH, and THF were obtained from a dry solvent system (alumina) and used without further drying. i -PrOH was distilled from Mg containing a small amount of I 2 . Et 3 N, pyridine, and 2,6-lutidine were distilled from and stored over KOH. TMSCl was distilled from quinoline prior to use. (COCl) 2 was distilled immediately prior to use. DMSO and EtCN were distilled from CaH 2 . ZnCl 2 was fused by exposure to flame under reduced pressure prior to use. Pd(PPh 3 ) 4 was synthesized 1 by a known method. CrCl 2 was dried by brief exposure to flame under reduced pressure. TiCl 4 was distilled from Cu powder immediately prior to use. All other reagents were used as supplied, unless otherwise noted. All reactions were carried out in oven-dried glassware, under a blanket of argon unless otherwise noted. Analytical thin layer chromatography was performed on Sorbent Technologies 0.20 mm silica gel 60 Å plates. Normal phase flash chromatography 2 was performed on Sorbent Technologies 32-63 μm 60 Å silica gel. Reverse phase flash chromatography 3 was performed on C18- functionalized silica gel (Aldrich). Melting points are uncorrected. Experimental Procedures and Spectroscopic Characterization of Novel Compounds (±)-1-(Triisopropylsilyl)hex-5-en-1-yn-3-ol (10). To a solution of aldehyde 9 4 (9.10 g, 43.3 mmol) in THF (111 mL, 0.400 M) at –20 °C was added dropwise, allylmagnesiumbromide (1.00 M solution in Et 2 O, 53.4 mL, 53.4 mmol, 1.20 equiv.). The reaction was stirred at -20 °C for 70 min. The reaction was quenched with sat. aq. NH 4 Cl, then warmed to ambient temperature. Et 2 O and H 2 O were added and (1) Hegedus, L. S. In Organometallics in Synthesis: A Manual; Schlosser, M., Ed.; John Wiley & Sons Ltd.: New York, 1994; Chapter 5, pp. 448. (2) Still, W. C.; Kahn, M.; Mitra, A. J. Org. Chem. 1978, 43, 2923-2925. (3) Farina, V. J. Org. Chem. 1991, 56, 4985-4987. (4) Journet, M.; Cai, D.; DiMichele, L. M.; Larsen, R. D. Tetrahedron Lett. 1998, 39, 6427-6428. CHO TIPS OH TIPS 10 9