Etoac

Solvents used for extraction, analytical thin-layer chromatography (TLC), column chromatography (CC) and fast centrifugal partition chromatography (FCPC), such as diethyl ether (Et₂O), ethyl acetate (EtOAc), n-hexane (Hex), dichloromethane (DCM) and ethanol (EtOH) were of analytical grade and were purchased from VWR Chemicals (Prolabo^®, Fontenay-sous-Bois, France). Water (H₂O), used for chromatographic separations, was of ultrapure grade and was produced by Milli-Q water (1.8 MΩ) equipment (Merck^®, KGaA, Darmstadt, Germany). Acetonitrile (ACN) and methanol (MeOH), used for high-performance liquid chromatography (HPLC), and chloroform, used to determine optical rotation values, were of HPLC grade and were purchased from VWR^® (Madrid, Spain). Deuterated chloroform (CDCl₃) was used to prepare solutions of isolated compounds for nuclear magnetic resonance (NMR) analysis and were purchased from VWR^® (Madrid, Spain). Acetic acid (AcOH), used for HPLC, was purchased from VWR^® (Madrid, Spain). Silica gel 60 F240 precoated aluminum sheets were purchased from Merck^® (Darmstadt, Germany). N-methylurea, used to prepare N-methyl-N-nitrosourea (see Supplementary Material), was purchased from Sigma-Aldrich^® (Madrid, Spain). Sodium hydroxide was purchased from VWR Chemicals^® (Prolabo, Fontenay-sous-Bois, France).

The entire solid cultures were sliced into small pieces with a flat spatula and transferred into 250 mL glass flasks. 100 mL of ethyl acetate (EtOAc, PESTINORM, VWR Chemicals, Leuven, Belgium) was added and the mixture was homogenized with an Ultra-Turrax at 19,000 rpm before filtering through a folded cellulose membrane filter (type 113P, Rotilabo^®ROTH, Karlsruhe). The filtrate was collected into a glass separating funnel and washed with 100 mL of Milli-Q^®water (Arium^®Lab water systems, Sartorius) to remove salts and water-soluble compounds. A total of 100 mL of crude EtOAc extract was collected and evaporated to dryness by a rotary evaporator (150 rpm at 40°C). Dried extracts were re-dissolved in 3 mL of UPLC/MS grade methanol (MeOH) and pipetted into a pre-weighed 4 mL-amber glass vial through a 13 mm syringe filter w/0.2 μm PTFE membrane (VWR International, Darmstadt, Germany). After drying the extracts under a nitrogen atmosphere, vials were weighed to determine the extract amount. The extracts were stored at -20°C.

cannabidiolic acid (CBDA), cannabigerolic acid (CBGA), cannabigerol (CBG), and cannabidiol (CBD) standard solutions (1 mg/mL in methanol or acetonitrile) were purchased from Cerilliant (Round Rock, TX, USA). Chrysoeriol was purchased from Sigma-Aldrich (Milan, Italy), while canniprene was kindly provided by Dr. Federica Pollastro of the Department of Drug Sciences of the University of Piemonte Orientale (Novara, Italy). Formic acid (HCOOH) and HPLC-grade solvents, including EtOH, MeOH, ACN, acetone, EtOAc, n-hexane, DCM, ethyl ether and toluene, were from VWR (Milan, Italy). H₂O was purified by using a Milli-Q Plus185 system from Millipore (Milford, MA, USA).

Softwood (SW) LignoBoost Kraft lignin as
a fine powder was kindly donated by Stora Enso (Finland). Ethyl acetate
(EtOAc, ≥99%), ethanol (EtOH, ≥99.8%), methanol (MeOH,
≥99.8%), acetone (≥99.5%), and hydrochloric acid (HCl,
37%) were purchased from VWR International. Lithium hydroxide (LiOH,
>98%), DAC (99%), tetrabutylammonium bromide (TBAB, 98%), cyclohexane
(99.5%), and trimethylolpropane tris(3-mercaptopropionate) (3TMP,
≥95%) were purchased from Sigma-Aldrich. Magnesium sulfite
(MgSO₄, 99%) was purchased from Thermo Scientific Chemicals.
Silastic T-2 base/curing agent (10:1 w/w) was used to prepare the
silicone molds. It was obtained from Dow Corning. All other chemicals
were purchased from Sigma-Aldrich and used as received.