*3.1. General Experimental Procedures*

Optical rotation was measured using a JASCO P-2000 polarimeter (Easton, MD, USA), UV/Vis data were obtained using a Beckman DU800 spectrophotometer (Brea, CA, USA), and IR spectra were recorded on a ThermoScientific Nicolet 6700 FT-IR spectrometer (Waltham, MA, USA). NMR experiments were conducted using a JEOL ECZ 500 NMR spectrometer (Akishima, Tokyo, Japan) equipped with a 3 mm inverse probe (H3X), a Bruker AVANCE III 600MHz NMR with a 1.7 mm dual tune TCI cryoprobe (Billerica, MA, USA), and a Varian VX500 (Palo Alto, CA, USA). NMR data were processed using Mestrenova (Mestrelab, Santiago de Compostela, Spain) and TopSpin (Bruker, Billerica, MA, USA). NMR data were recorded in CDCl3 and referenced to the solvent peak (7.260, 77.160). For the low-resolution LC-MS/MS analysis, a ThermoFinnigan Surveyor HPLC System (San Jose, CA, USA) with a Phenomenex Kinetex 5 μm C18 100 × 4.6 mm column (Torrance, CA, USA) coupled to a ThermoFinnigan LCQ Advantage Max Mass Spectrometer (San Jose, CA, USA) in positive ion mode was used. Samples were analyzed using one of two linear gradients from 30% CH3CN + 0.1% formic acid to 99% CH3CN + 0.1% formic acid in H2O + 0.1% formic acid at a flow rate of either 0.6 mL/min or 0.7 mL/min over 32 min or 30 min, respectively. Samples were run at a concentration of 1 mg/mL, with concentrations increased up to 4 mg/mL in situations where the peak intensities were insufficient. For the HiRes-ESI-MS analysis, an Agilent 6230 time-of-flight mass spectrometer (TOFMS) (Santa Clara, CA, USA) with Jet Stream ESI source was used. For HiResMS<sup>2</sup> fragmentation data, a ThermoScientific Orbitrap XL mass spectrometer (Waltham, MA, USA) with direct infusion of the sample into the Thermo IonMax electrospray interface was used.

Compound isolation was performed using two semi-preparative HPLCs: a Thermo Scientific Dionex UltiMate 3000 HPLC (Waltham, MA, USA) system with automated fraction collector, a Waters HPLC system with 1500 series pumps (Milford, MA, USA), and a 996 photodiode array detector with manual fraction collection. HPLC separation was performed using a Phenomenex Kinetex 5 μm C18 10 × 150 mm column (Torrance, CA, USA) and reverse phase gradients of acetonitrile in H2O, with both solvents containing 0.1% (*v*/*v*) formic acid. HPLC grade organic solvents and Millipore Milli-Q system (Burlington, MA, USA) purified water were used.

All reagents, catalysts, and solvents used for the synthetic experiments were purchased in their purest and driest form. All experiments were carried out under an inert atmosphere (Ar) unless otherwise specified.

National Cancer Institute (NCI) H460 hypotriploid human cells [American Type Culture Collection (ATCC) HTB-177] and RAW 264.7 murine macrophages (ATCC TIB-71) were purchased from the ATCC (Manassas, VA, USA).
