S1 Total Synthesis and Initial Biological Evaluation of New B-Ring Modified Bryostatin Analogs Paul A. Wender,* Joshua C. Horan, Vishal A. Verma Department of Chemistry and Department of Molecular Pharmacology, Stanford University, Stanford, CA 94305-5080 Supporting Information General Methods. All glassware used was oven-dried (>130 ºC) and cooled under N 2 . Stirring was accomplished via magnetic, Teflon ® -coated stir bars that were oven-dried and cooled under N 2 . Reactions were sealed with rubber septa or caps and maintained in an inert environment under N 2 (passed through calcium sulfate). Solid reagents were measured on a Mettler AK160 or AG104 balance. Air and moisture sensitive liquids were transferred via dry syringes. Reaction temperatures refer to the temperature that the reaction glassware was immersed. Room temperature is generally between 23 – 25 ºC. Higher temperatures, unless otherwise indicated, were achieved by the use of a silicon oil bath heated by a nichrome wire under constant voltage. Temperatures of 0 ºC and –78 ºC were maintained by the use of an ice bath and dry ice/acetone bath respectively. The term in vacuo refers to the use of a rotary evaporator with an attached vacuum membrane pump. Tetrahydrofuran, diethyl ether, toluene, and dichloromethane were passed through alumina drying columns (Solv-tek Inc.) unless otherwise indicated. Petroleum ether, ethyl acetate, and pentane was purchased from Fisher Chemical. Deuterated solvents were purchased from Cambridge Isotope Laboratories. Deuterated chloroform was stored over anhydrous potassium carbonate. Reagents were used as purchased unless otherwise indicated. Analytical TLC was performed using 0.25 mm silica gel 60F 254 coated plates from EMD Chemicals Inc. and monitored at 254 nm. Staining was accomplished using p-anisaldehyde, potassium permanganate, or cerium sulfate and gentle heating. Preparative flash chromatography was performed by running solvent under a pressure of air through silica gel (230-400 mech, 60 Å), purchased from Silicycle Chemical Division. Reverse phase high pressure liquid chromatography (RP-HPLC) was performed on a Varian ProStar 320 and monitored at 220 nm. The column used was an Alltech Alltima C18 (10 μm) column (length: 250 mm, inner diamter: 10.0mm). Solvent was removed via lyophilization using a Virtis Freezemobile 25EL lyophilizer. Optical rotations were measured using a JASCO DIP-360 digital machine. The format for measurements are: [α] e temperatur D = specific rotation in degrees (c = concentration in g/100 mL, solvent). Nuclear magnetic resonance spectra were taken on a Varian Inova 600 ( 1 H at 600