Supporting Information for: Enabling a Diversity-Oriented Catalytic Atom Looping of a Biobased Polycarbonate

S1 Supporting Information for: Enabling a Diversity-Oriented Catalytic Atom Looping of a Biobased Polycarbonate Enrico Lanaro,[a][b][c] Thirusangumurugan Senthamarai,[a] Stephen K. Hashmi[c] and Arjan W. Kleij*[a][d] [a] Institute of Chemical Research of Catalonia (ICIQ), the Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007 Tarragona, Spain [b] Departament de Química Física i Inorgánica, Universitat Rovira i Virgili, Marcel·lí Domingo s/n, 43007 Tarragona, Spain [c] Institut für Organische Chemie, Heidelberg University, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany [d] Catalan Institute of Research and Advanced Studies (ICREA), Pg. Lluis Companys 23, 08010 Barcelona, Spain *E-mail: [email protected] S2 Table of Contents 1. General experimental details .................................................................................................... 3 1.1 General remarks .................................................................................................................. 3 1.2 Reagents and complexes ..................................................................................................... 4 2. Polymerization procedures ....................................................................................................... 5 2.1 Synthesis of poly(menthene carbonate), PMC, via ROCOP ................................................ 5 2.2 Synthesis of poly(menthene carbonate), PMC, via ROP ..................................................... 5 2.3 Additional information and data for the polymerization studies ....................................... 6 3. Depolymerization procedures ................................................................................................... 8 3.1 General procedure for the TBD-initiated depolymerization of PLC into MO ...................... 8 3.2 General procedure for the TBD-initiated depolymerization of PLC into MC ...................... 8 3.3 General procedure for the TBD-initiated depolymerization of PLC into MC ...................... 9 3.4 Additional information on the depolymerization studies ................................................. 10 4. Diversification studies using MO as a precursor ..................................................................... 20 5. Diversification studies using MC as synthon ........................................................................... 23 6. Diversification studies using MD as synthon........................................................................... 25 7. Synthesis of new types of bifunctional monomers ................................................................. 28 8 Characterization data for all compounds ................................................................................. 30 9. References ............................................................................................................................... 82 S3 1. General experimental details 1.1 General remarks All oxygenand water-sensitive operations were carried out under a nitrogen atmosphere using an MBraun glovebox and Schlenk techniques. All reagents were purchased from Aldrich or TCI suppliers and used as received if not stated differently. Solvents were dried using an Innovative Technology PURE SOLV solvent purification system. Benzyl alcohol (BnOH) was dried over calcium hydride (CaH2) and distilled under reduced pressure. Nuclear magnetic resonance (NMR) spectroscopy: NMR spectra were obtained on a Bruker Avance II 400 MHz or a Bruker Avance II 500 MHz spectrometer at room temperature in the respective deuterated solvents. 1H and 13C chemical shifts are reported in parts per million (ppm), relative to tetramethylsilane (TMS) for 1H and 13C with the residual solvent peak used as an internal reference. Multiplicities are reported as follows: singlet (s), broad band (br), d (doublet), dd (doublet of doublets), triplet (t) and multiplet (m). Thermal analyses: Differential scanning calorimetry (DSC) to determine glass transition temperatures (Tg) were measured under an N2 atmosphere using a Mettler Toledo model DSC822e. Samples were weighed into 40 μL aluminum crucibles and subjected to three heating cycles typically at a heating rate of 10 °C/min. Thermogravimetric analyses (TGA) were recorded under an N2 atmosphere using Mettler Toledo model TGA/SDTA851. Samples were weighed into 40 μL aluminum crucibles and heated to 600 °C typically at a heating rate of 10 °C/min. All thermal data were collected by the Research Support Unit at ICIQ. For the DSC analyses, typically the data referring to the second heating/cooling were selected to determine the Tg values. Gel permeation chromatography (GPC) measurements were performed using an Agilent 1200 series HPLC system, equipped with a PSS SDV Analytical linear M GPC column (8 x 300 mm; 5 μm particle size) in tetrahydrofuran (THF) at 30 °C at a flow rate of 1 mL·min−1. Samples were analyzed at a concentration of 1 mg·mL−1 after filtration through a 0.45 μm pore-size membrane. Mn, Mw, and Đ data were derived from the RI signal by a calibration curve based on polystyrene standards (PS from Polymer Standards Service) for the analysis of the polymers. The GPC samples were prepared by dissolving the polymer (2−5 mg) in THF (2 mL) and filtering the solution through a 0.45 μm pore-size membrane. S4 1.2 Reagents and complexes Menthene oxide (MO) was prepared according to a previously reported procedure,[1] and was used after being stirred over CaH2 for 24 hours followed by filtration. Bis-(triphenylphosphine)-iminium chloride (PPNCl) was purified by crystallization from chloroform. The Al-complex (AlMe)[2] and menthene diol were prepared according to previously reported procedures.[3] 1.3 Menthene cyclic-carbonate (MC) monomer synthesis An oven-dried 50 mL flask under argon was charged with menthene diol (MD) (11.0 g, 64 mmol, dr > 20:1) dissolved in 30 mL of dry DCM. Then, to the reaction mixture (0 °C) were sequentially added pyridine (20 g, 21 mL, 0.26 mol, 4 equiv) and dropwise a solution of triphosgene (9.5 g, 32 mmol, 0.5 equiv) in 80 mL of DCM. The reaction mixture was stirred at 0 °C for 4 hours, and the reaction mixture quenched with a saturated solution of NaHCO3 (150 mL) and diluted with DCM. The organic phase was washed with 1 N HCl (3 × 100 mL), a saturated solution of NaHCO3 (3 × 100 mL) and brine (3 × 100 mL). The organic phase was then dried on MgSO4, filtered and concentrated under reduced pressure. The residue was purified via column chromatography (cyclohexane:ethyl acetate, 99:1 to 95:5), obtaining the product as colorless crystals (9.47 g, 75% yield, dr > 20:1). 1H NMR (400 MHz, CDCl3) δ 4.62 – 4.46 (m, major), 3.92 – 3.85 (m, minor), 3.74 – 3.66 (m, minor), 2.59 – 2.47 (m, 1H), 2.02 – 1.42 (m, 6H), 1.09 – 0.99 (m, 6H), 0.94 – 0.90 (m, 3H). 13C NMR (101 MHz, CDCl3) δ 154.8, 80.5, 80.0, 43.6, 30.2, 25.3, 24.9, 22.2, 22.0, 21.7, 10.7. HRMS (ESI/TOF) m/z: [M + Na]+ Calcd for. C11H18NaO3: 221.1150; found 221.1148. S5 2. Polymerization procedures 2.1 Synthesis of poly(menthene carbonate), PMC, via ROCOP Menth-2-ene oxide synthetized according to a previously reported procedure[1] was dried prior to its use on CaH2 and filtered. In a nitrogen-filled glovebox, the menth-2-ene oxide, AlMe, PPNCl and dry toluene were combined in a Teflon vessel equipped with a cross-shaped magnetic stirring bar, and placed inside a stainlesssteel reactor. The reactor was purged three times with 5 bar of CO2. Finally, the pressure was stabilized at the desired pressure of CO2 at r.t. After placing the reactor in a metal heating block, the reaction mixture was stirred at the stated temperature and time. The reaction was stopped by cooling the reactor in an ice bath and subsequent applying gentle depressurization. When opened, an aliquot of the product was dissolved in a minimum amount of DCM, and the solvent removed in vacuo following analysis by 1H-NMR analysis to determine the substrate conversion. The remaining reaction mixture was added dropwise to a stirred solution of MeOH/HCl (1 M) (12:1 v/v) causing the PMC product to precipitate as a white solid. The precipitate was filtered, washed with cold methanol and dried in vacuo. 2.2 Synthesis of poly(menthene carbonate), PMC, via ROP In a nitrogen-filled glovebox, cyclic trans-menthene carbonate (80 mg, 0,04 mmol), benzyl alcohol, TBD and toluene were combined in a vial with a Teflon screw cap. The reaction mixture was stirred heated with an oil bath to the desired reaction temperature and kept for the indicated time. The reactions were quenched by cooling to ambient temperature and then taking an aliquot dissolving it a minimum amount of DCM. The latter was removed by evaporation, and the residue analyzed by 1H NMR to determine the conversion. The remaining reaction mixture was added dropwise to a stirred solution of MeOH/HCl (1 M, 7 mL, 12:1 v/v) causing the PMC to precipitate as a white solid. This solid was separated via decantation and vacuum dried. S6 2.3 Additional information and data for the polymerization studies Ring-opening copolymerization (ROCOP) of menthene oxide (MO) and CO2. Table S1. Optimization of the reaction conditions for the ROCOP of menthene oxide and CO2. Entrya Time (h) Al-Me (equiv) PPNCl (equiv) T (°C) Conversion (%)b Yield (%)c Mn (Kg/mol)d Đd Tge (°C) Td5 f (°C) 1 72 0,01 0,005 45 20a 49 5.5 1,28 136 218 2 72 0,01 0,005 45 51 37 3.8 1.25 126 210 3 24 0,01 0,005 45 21 13 2.8 1.16 99 243 4 48 0,01 0,005 45 40 31 2.9 1.26 109 215 5 72 0.01 0.0025 45 26 18 3.0 1.22 - - 6 72 0.005 0.005 45 33 - 2.9 1.27 - - 7g 72 0,01 0,005 45 64 - 4.2 1.28 - - 8h 24 0.01 0.005 45 26 - 3.5 1.23 - - 9h 72 0.01 0.005 45 56 - 5.1 1.32 - - 10 24 0.01 0.005 60 60 58 7.0 1.22 133 225 11 24 0.01 0.005 30 8 - 2.6 1.10 - - 12h 24 0.01 0.005 60 70 - 3.7 1.23 - - aReaction conditions: MO = menthene oxide (1.5 g, 9.7 mmol), toluene (0.38 mL), CO2 (15 bar). bDetermined by 1H NMR (CDCl3). cIsolated yield. dDetermined by GPC. eDetermined by DSC analysis. fDetermined by TGA analysis. gCO2 (30 bar). hNeat conditions. S7 Ring opening polymerization (ROP) study of menthene cyclic-carbonate (MC). Table S2. Optimization of the reaction conditions for the ROP of menthene cyclic-carbonate. Entrya Time (h) TBD (equiv) BnOH (equiv) T (°C) Conversion (%)b Mn (Kg/mol)c Đc 1 48 0.02 0,02 80 91 2.8 1.64 2 48 0.01 0,01 80 76 3.0 1.61 3 48 0.02 0,01 80 92 3.2 1.67 4 48 0.02 0.01 50 79 3.3 1.47 5 24 0.02 0.01 50 52 2.4 1.21 6 48 0.02 0.01 23 32 2.1 1.11 7 48 0.02 0 80 93 3.4 1.87 8 24 0.02 0,01 80 89 3.2 1.66 9 5 0.02 0,01 80 41 2.4 1.24 10 24 0.02 0 80 88 3.4 1.75 11d 24 0.02 0 80 91e 5.9 1.76 12d 5 0.02 0 80 86 4.3 1.80 13f 24 0.02 0 80 77 3.3 1.94 14g 24 0.02 0 80 92 4.7 1.61 aReaction conditions: MC = menthene cyclic carbonate (80 mg, 0.4 mmol), toluene (1.0 M). bDetermined by 1H NMR (CDCl3). cDetermined by GPC. dToluene (4.0 M). eIsolated yield = 84%, Tg = 121 °C (determined by DSC analysis), Td5 = 275 °C (determined by TGA analysis) and DSC. fNeat conditions. gToluene (8.0 M). S8 3. Depolymerization procedures 3.1 General procedure for the TBD-initiated depolymerization of PLC into MO In a nitrogen-filled glovebox, a 10 mL sealed tube was introduced containing PMC (80 mg, 0.40 mmol) and 0.80 mL of a solution of TBD in ACN (52.7 mg/5 mL). The reaction mixture was stirred under reflux (using an oil bath) for 72 hours. The mixture was then concentrated in vacuo and purified via column chromatography (cyclohexane:ethyl acetate, 95:5 v/v) obtaining the purified product MO (58 mg, 92% yield, dr = 7:3). NB. A scale up using 500 mg of PMC was performed following the same procedure, with a scaling factor of 10 (90% isolated yield, dr = 7:3). 3.2 General procedure for the TBD-initiated depolymerization of PLC into MC In a nitrogen-filled glovebox, a 10 mL sealed tube was introduced containing PMC (50 mg, 0.25 mmol) and 0.5 mL of a solution of TBD in ACN (42.1 mg/2 mL). The reaction mixture was stirred under reflux (oil bath) for 1 hour. The reaction mixture was then concentrated under vacuum, dissolved in a minimum amount of DCM and then slowly added to a solution of MeOH/HCl (12:1 v/v). The precipitated PMC (7.7 mg) was recovered by decantation. The decanted solution was concentrated under vacuum and the residue purified by column chromatography (cyclohexane:ethyl acetate (8:2 to 6:4 v/v) obtaining MC (23.8 mg, 78% isolated yield brsm, dr = 2:1) and the remaining PMC (9.2 mg, total recovered PMC yield busm = 90%). NB. A scale up at 500 mg of PMC was performed following the same procedure (scaling factor of 10) giving MC with a 72% isolated yield brsm, dr = 2:1, and the recovered PMC busm was 95%. S9 3.3 General procedure for the TBD-initiated depolymerization of PLC into MC In a 10 mL sealed tube were mixed PMC (50 mg, 0.25 mmol), H2O (9.1 mg, 2 equiv), NaOH (3.0 mg, 0.3 equiv) and 0.50 mL of a solution of TBD in ACN (52.7 mg/5 mL). The reaction mixture was stirred under reflux (oil bath) for 48 hours. The reaction mixture was concentrated under vacuum, neutralized with HCl (1 M) and extracted with ethyl acetate. The crude product was then purified via column chromatography (cyclohexane:ethyl acetate, 9:1 to 7:3) obtaining the purified product MD (40.7 mg, 94% yield). NB. scale up at 500 mg of PMC was done following a previously reported procedure (94% isolated yield, dr = 4:1).[4] S16 Table S9. Screening of other (organo)catalysts for the depolymerization of PMC. Entrya Catalyst Time (h) PMC (%)b MC (%)b MO (%)b 1 TBD 24 19 29 52 72 0 13 86 2 DBU 24 94 3 3 72 55 3 42 3 KHMDS 24 62 7 31 72 40 13 47 4 n-Bu4NN3 24 99 0 0 72 97 1 2 aReaction conditions: PMC (50 mg, 0.25 mmol). bDetermined by 1H NMR (CDCl3). S17 Table S10. Study of the influence of different reaction conditions towards a selective formation of MD catalyzed by TBD in the presence of H2O. Entrya Time (h) T (ºC) TBD (mol%) H20 (equiv) PMC (%)b MD (%)b MC (%)b MO (%)b 1 24 80 15 1 67 25 5 3 2 72 80 15 1 48 43 4 5 3 24 80 10 2 79 19 2 0 4 72 80 10 2 62 37 1 0 5 72 110 10 2 14 79 0 7 6 24 110 15 2 5 86 0 9 7 48 110 15 2 0 91c 0 9 8d 48 110 15 2 0 >95e 0 <5 9 72 110 15 2 0 90 0 10 10 24 110 15 10 37 55f 0 8 aReaction conditions: PMC (50 mg, 0.25 mmol). bDetermined by 1H NMR (CDCl3). cIsolated yield = 86%, dr = 4:1. dReaction carried out using NaOH (30 mol%). eIsolated yield was 94%, dr = 4:1. S18 Table S10. Study of the influence of the reaction conditions on the selective formation of MD catalyzed by TBD in MeOH. Entrya T(ºC) Time (h) PMC (%)b MD (%)b MC (%)b MO (%)b 1 110 6 6 72 0 22 2 110 24 0 74 0 26 3 80 6 40 11 0 49 4 80 24 16 68 0 16 5c 80 24 7 74 0 17 aReaction conditions: PMC (50 mg, 0.25 mmol). bDetermined by 1H NMR (CDCl3). cReaction carried out with NaOH (30 mol%). S19 Control experiments: PMC (80 mg, 0.4 mmol) in dry ACN (0.50 M) at 110 °C, without TBD: No observable depolymerization was noticed after 24 h. The polymer did not dissolve in ACN even at high temperatures, and a pellet was formed. MC (80 mg, 0.4 mmol) in dry ACN (0.50 M) at 110 °C, without TBD: After 72 h, no reaction was observed by 1H NMR, while the MC does not decompose and no signs of epoxide or diol were noted. S20 4. Diversification studies using MO as a precursor * For each product, only the major isomer is shown * Synthesis of chlorohydrin 1 2-Menthene-oxide (1.08 g, 7.00 mmol), DCM (70 mL) and HCl (36% aqueous, 21 mL) were stirred together for 4 h at room temperature. Then, the mixture was washed with saturated NaHCO3, brine and dried over Na2SO4. The organic solvent was evaporated under reduced pressure and the residue was purified via column chromatography (hexane:ethyl acetate, 9:1 v/v), obtaining the purified product as a yellowish oil (1.28 g, 96% yield, rr = 7:3). 1H NMR (400 MHz, CDCl3) δ 4.33 – 4.28 (m, major), 4.16 – 4.07 (m, minor), 3.85 (s, major), 2.20 – 2.05 (m, 1H), 1.70 – 1.59 (m, 2H), 1.55 – 1.34 (m, 3H), 1.30 – 1.24 (m, 2H), 1.03 – 0.91 (m, 9H). 13C NMR (101 MHz, CDCl3) δ 74.8, 64.0, 42.1, 29.5, 29.2, 27.7, 23.8, 20.8, 20.1, 17.7. HRMS (ESI/TOF) m/z: [M - H]- Calcd. for C10H18ClO: 189.1041; found 189.1038. FT-IR (neat)  (cm-1) 3416. Synthesis of alkynylated compound 2 A solution of phenyl acetylene (248 mg, 2.43 mmol, 1.5 equiv) in anhydrous THF (50 mL) was cooled to −78 °C under a nitrogen atmosphere. To this solution, nbutyllithium (2.5 M in hexanes, 0.972 mL, 7.5 mmol, 1.5 equiv) was added dropwise for 30 minutes at −78 °C. Menthene oxide (250 mg, 1.62 mmol) was then added to the reaction mixture, followed by boron trifluoride diethyl etherate (35 mg, 2.43 mmol, 1.5 equiv), maintaining the temperature at −78 °C. The reaction mixture was stirred at this temperature for an additional 4 h. Upon completion, the reaction was quenched by the careful addition of saturated aqueous ammonium chloride solution. The resulting mixture was extracted with ethyl acetate (3 × 20 mL), and the combined organic layers were washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by flash column chromatography on silica gel (hexane /ethyl acetate (4:1 v/v) to yield the desired product as a colorless oil (356 mg, 86% yield, rr = 2:1, dr = 5:1). 1H NMR (400 MHz, CDCl3) δ 7.46 – 7.36 (m, 2H), 7.34 – 7.23 (m, 3H), 4.34 – 4.29 (m, minor), 4.24 – 4.20 (m, minor), 3.96 – 3.91 (m, major), 3.87 – 3.82 (m, minor), 3.20 – 3.13 (m, major), 2.95 – 2.90 (m, minor), 2.15 – 1.97 (m, 1H), 1.80 – 1.27 (m, 6H), 1.10 – 0.93 (m, 9H). 13C NMR (101 MHz, CDCl3) δ 131.7, 128.3, 128.3, 127.8, 124.1, 124.0, 89.1, 88.8, 84.9, 84.5, 77.5, 77.4, 77.2, 76.8, 74.8, 74.3, 71.1, 64.2, 43.3, 42.4, 42.2, 40.5, 38.7, 38.3, 32.1, 31.8, 31.6, 31.4, 30.7, 30.3, 30.2, 29.8, 29.8, 29.8, 29.6, 29.5, 29.3, 29.2, 28.5, 28.1, 27.8, 26.2, 24.2, 23.9, 22.8, 21.2, 21.1, 21.0, 20.9, 20.8, 20.2, 20.0, 18.3, 17.8, 14.3. HRMS (ESI/TOF) m/z: [M + H]+ Calcd. for C18H25O: 257.1900; found 257.1891. FT-IR (neat)  (cm-1) 3426, 754, 690. Synthesis of 1,2-azido-alcohol 3 2-Menthene-oxide (155 mg, 1.00 mmol), ammonium chloride (108 mg, 2.01 mmol) and NaN3 (523 mg, 8.04 mmol) were mixed together in a MeOH and water solution (0.30 M, 8:1 v/v). The reaction mixture was stirred for 18 h at room temperature. The solvent was evaporated, water was added and the mixture was extracted with ethyl acetate (4 × 25 mL). The organic layers were combined, washed with brine and dried over Na2SO4. The solvent was removed under reduced pressure and the residue was purified via column chromatography (hexane: ethyl acetate, 95:5 v/v), obtaining the purified product as a colorless oil (141 mg, 71% yield, rr = 7:3). 1H NMR (400 MHz, CDCl3) δ 4.10 (s, minor), 3.93 – 3.79 (m, major), S21 3.62 – 3.54 (m, minor), 2.04 – 1.77 (m, 1H), 1.67 – 1.48 (m, 3H), 1.45 – 1.12 (m, 4H), 1.01 – 0.90 (m, 9H). 13C NMR (101 MHz, CDCl3) δ 72.5, 64.5, 41.1, 30.6, 29.1, 27.5, 24.3, 20.9, 20.7, 17.6. HRMS (ESI/TOF) m/z: [M + H – N2]+ Calcd. for C10H20NO: 170.1539; found 170.1545. FT-IR (neat)  (cm-1) 3427, 2093. Synthesis of 1,2-amino-alcohol 4 2-Menthene-oxide (100 mg, 648 µmol) and imidazole (110 mg, 1.62 mol) were stirred in a vial at 70 °C for 72 h. The mixture was then purified via preparative TLC (DCM:MeOH, 95:5 v/v) obtaining the product as a white solid in 78% yield (rr = 2:1). 1H NMR (400 MHz, CDCl3) δ 7.65 – 7.53 (m, 1H), 7.13 – 6.97 (m, 2H), 4.49 (t, J = 3.8 Hz, 1H, major), 4.24 – 4.22 (m, 1H, minor), 4.04 – 4.02 (m, 1H, minor), 3.73 – 3.69 (m, 1H, major), 2.30 (dd, J = 12.6, 6.9 Hz, 1H), 1.93 – 1.84 (m, 1H), 1.79 – 1.70 (m, 1H), 1.64 – 1.43 (m, 3H), 1.32 – 1.23 (m, 2H), 0.98 – 0.91 (m, 3H), 0.85 – 0.72 (m, 6H). 13C NMR (101 MHz, CDCl3) δ 138.2, 128.7, 120.3, 74.5, 60.8, 40.3, 30.6, 28.8, 26.8, 25.6, 21.1, 20.7, 17.8. HRMS (ESI/TOF) m/z: [M + H]+ Calcd. for C13H23N2O: 223.1805; found 223.1810. FT-IR (neat)  (cm-1) 3175, 2956, 2928, 2871. Synthesis of alcohol 5 To a stirred solution of menthene oxide (250 mg, 1.62 mmol) in dry toluene (5 mL) under a nitrogen atmosphere, triphenylantimony (24 mg, 0.081 mmol, 0.05 equiv) was added. Subsequently, trimethylaluminum (116 mg, 1.62 mmol, 2.0 M solution in toluene) was added dropwise via a syringe. The reaction mixture was stirred at room temperature for 32 h. After completion, the reaction was carefully quenched with 5 mL of 1 N aqueous HCl. The organic and aqueous layers were separated, and the aqueous phase was extracted twice with diethyl ether (10 mL). The combined organic extracts were dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude residue was purified by flash column chromatography on silica gel using hexanes/ethyl acetate (99:1, v/v) as the eluent to afford the desired product as a colorless oil (205 mg, 74% yield, rr = 7:3). 1H NMR (400 MHz, CDCl3) δ 3.84 (s, minor), 3.54 (s, major), 2.17 – 1.90 (m, 1H), 1.88 – 1.61 (m, 2H), 1.59 – 1.24 (m, 5H), 1.16 – 1.04 (m, 1H), 1.00 – 0.78 (m, 12H). 13C NMR (101 MHz, CDCl3) δ 77.11, 40.40, 37.04, 30.19, 29.27, 28.44, 24.04, 21.45, 20.56, 18.30, 11.12. HRMS (ESI/TOF) m/z: [M + Na]+ Calcd. for C11H22NaO: 193.1569; found 193.1563. FT-IR (neat)  (cm-1) 3403. Synthesis of oligoester 6 In a nitrogen-filled glovebox, 2-menthene oxide MO (200 mg, 1.30 mmol), phthalic anhydride (96 mg, 0,65 mmol) and a binary catalyst (1.0 mol% of FeMe complex, analogue of AlMe, and PPNCl as initiator, 0.50 mol%)[5] were placed in an oven-dried 4 mL vial and the vial was sealed with a Teflonlined cap. The reaction mixture was then removed from the glovebox and placed in oil bath at 25 °C for 48 h. Then, the volatiles were removed under vacuum. The crude product was dissolved in a minimal amount of DCM and precipitated with a solution of HCl (1 M) in methanol. Finally, the polymer was washed with methanol and dried under vacuum obtaining a white powder (159 mg, 81% yield). 1H NMR (400 MHz, CDCl3) δ 8.11 – 7.29 (m, 4H), 5.74 – 4.81 (m, 2H), 2.16 – 0.75 (m, 16H). 13C NMR (101 MHz, CDCl3) δ 166.5, 166.2, 165.6, 132.6, 132.0, 131.2, 131.0, 130.5, 129.0, 85.4, 80.8, 77.5, 77.4, 77.16, 76.8, 76.5, 73.7, 73.6, 73.4, 73.2, 71.6, 71.3, 71.0, 47.8, 47.8, 47.1, 42.2, 41.8, 37.1, 36.1, 36.0, 32.5, 32.2, 32.0, 30.7, 30.6, 30.4, 29.0, 28.6, 28.5, 26.4, S22 25.7, 25.6, 25.5, 24.9, 24.5, 23.8, 22.7, 22.3, 21.1, 21.1, 21.0, 21.0, 20.9, 20.9, 18.4, 18.2, 18.1, 17.7, 17.6, 17.6, 16.2, 16.1, 16.0, 16.0, 15.9. S23 5. Diversification studies using MC as synthon Synthesis of thiocarbonate 7 Menthene cyclic-carbonate (104 mg, 514 µmol), 4-methoxyphenyl methanethiol (150 mg, 976 µmol) and TBD (14 mg, 101 µmol) were mixed in a vial under Argon. The reaction mixture was stirred for 18 h at 40 °C. The crude product was purified via column chromatography (hexane:ethyl acetate, 95:5 to 8:2 v/v) obtaining the product as a colorless oil (142 mg, 78% yield, rr = 1:1). 1H NMR (400 MHz, CDCl3) δ 7.28 – 7.22 (m, 2H), 6.87 – 6.81 (m, 2H), 5.21 – 5.17 (m, 0.5H), 5.00 – 4.95 (m, 0.5H), 4.07 (s, 2H), 4.04 – 4.00 (m, 0.5H), 3.81 – 3.74 (m, 3H + 0.5H), 2.05 – 1.95 (m, 0.5H), 1.71 – 1.42 (m, 5H + 0.5H), 1.33 – 1.23 (m, 2H), 0.97 – 0.87 (m, 9H). 13C NMR (101 MHz, CDCl3) δ 170.7, 170.5, 159.0, 130.0, 129.9, 129.0, 128.9, 114.1, 79.5, 70.8, 68.1, 55.3, 42.4, 40.6, 35.0, 35.0, 30.8, 29.4, 28.7, 28.6, 28.4, 27.3, 24.3, 23.4, 21.1, 20.9, 20.8, 20.6, 17.4. HRMS (ESI/TOF) m/z: [M + Na]+ Calcd. for C19H28NaO4S: 375.1601; found 375.1615. FTIR (neat)  (cm-1) 3506, 1704. Synthesis linear of carbonate 8 In a nitrogen-filled glove-box, menthene cyclic-carbonate (100 mg, 504 µmol), BnOH (60 mg, 555 µmol) and TBD (14 mg, 101 µmol) were mixed in a vial. The reaction mixture was stirred for 18 h at 40 °C. The crude product was purified via column chromatography (hexane:ethyl acetate, 9:1 v/v) obtaining the purified product as a colorless oil (111 mg, 72% yield, rr = 1:1). 1H NMR (400 MHz, CDCl3) δ 7.43 – 7.29 (m, 5H), 5.20 – 5.13 (m, 2H), 4.95 – 4.92 (m, 0.5H), 4.73 – 4.69 (m, 0.5H), 4.04 – 4.00 (m, 0.5H), 3.81 – 3.72 (m, 0.5H), 2.07 – 1.96 (m, 0.5H), 1.78 – 1.75 (m, 0.5H), 1.69 – 1.61 (m, 1H), 1.60 – 1.40 (m, 3H), 1.37 – 1.24 (m, 3H), 0.95 – 0.89 (m, 9H). 13C NMR (101 MHz, CDCl3) δ 155.2, 155.0, 135.4, 135.4, 128.6, 128.6, 128.5, 128.5, 128.2, 80.1, 70.8, 69.6, 69.6, 68.0, 42.3, 40.6, 30.7, 29.2, 28.6, 28.6, 28.4, 27.3, 24.2, 23.4, 21.1, 20.9, 20.8, 20.6, 17.4, 17.2. HRMS (ESI/TOF) m/z: [M + Na]+ Calcd for C18H26NaO4: 329.1723; found 329.1733. FT-IR (neat)  (cm-1) 3490, 1740. Synthesis of carbamate 9 Into a glove-box, menthene cyclic-carbonate (102 mg, 514 µmol), morpholine (56 mg, 640 µmol) and TBD (14 mg, 101 µmol) were mixed in a vial. The reaction mixture was stirred for 18 h at 40 °C. The crude product was purified via column chromatography (hexane:ethyl acetate, 9:1 to 8:2 v/v) obtaining the product as a colorless oil (144 mg, 98% yield, rr = 1:1). 1H NMR (500 MHz, CDCl3) δ 5.00 – 4.95 (m, 0.5H), 4.76 (t, J = 3 Hz, 0.5H), 4.01 – 3.97 (m, 0.5H), 3.77 – 3.71 (m, 0.5H), 3.71 – 3.57 (m, 4H), 3.53 – 3.38 (m, 4H), 2.11 – 2.00 (m, 1H), 1.77 (s, 1H), 1.71 – 1.57 (m, 2H), 1.50 – 1.17 (m, 4H), 0.96 – 0.87 (m, 9H). 13C NMR (126 MHz, CDCl3) δ 155.26, 154.93, 74.55, 70.89, 68.11, 66.64, 42.88, 40.55, 31.00, 29.23, 29.11, 29.06, 28.62, 27.53, 24.93, 23.56, 21.18, 20.97, 20.78, 17.57. HRMS (ESI/TOF) m/z: [M + Na]+ Calcd. for C15H27NNaO4: 308.1832; found 308.1846. FT-IR (neat)  (cm-1)3454, 1676. S24 Synthesis of bis-borate ester 10 Menthene cyclic-carbonate (198 mg, 1 mmol) and HBpin (397 mg, 3.1 mmol) were dissolved in dry toluene (1.2 mL) in an oven-dried flask under argon. Then, di-n-butyl-magnesium (1 M in heptane, 4.2 mg, 30 µmol) was added and the reaction mixture was stirred at 70 °C for 18 h. The solvent was removed under reduced pressure obtaining the product as a colorless viscous oil (91% 1H-NMR yield using mesitylene as internal standard). 1H NMR (400 MHz, CDCl3) δ 4.39 – 4.29 (m, 1H), 4.09 – 3.99 (m, 1H), 2.02 – 1.84 (m, 1H), 1.56 – 1.51 (m, 1H), 1.35 – 1.26 (m, 29H), 1.01 – 0.82 (m, 9H). 13C NMR (101 MHz, CDCl3) δ 83.3, 82.8, 82.7, 76.3, 74.1, 73.9, 73.4, 70.7, 41.7, 41.6, 41.5, 30.2, 30.1, 30.0, 28.8, 28.5, 28.5, 28.0, 27.9, 27.8, 25.0, 24.9, 24.8, 24.7, 24.7, 24.6, 24.6, 24.6, 24.6, 23.8, 23.7, 23.6, 21.3, 21.2, 21.1, 20.9, 20.7, 17.7, 17.6, 17.6. FT-IR (neat)  (cm-1) 2976, 2931, 2872, 1499, 1424. Note that the product cannot be columned due to its instable character, see reference [6] for further details. S25 6. Diversification studies using MD as a precursor Synthesis of bis-aldehyde 12 NaIO4 (186 mg, 871 µmol), silica (0.50 g), water (2.3 mL) and DCM (4 mL) were mixed in a vial. Under vigorous stirring, a solution of trans-menthene-diol (100 mg, 580 µmol) in DCM (3 mL) was added dropwise. The reaction mixture was stirred for 18 h at 40 ºC, then filtered (the silica was rinsed with DCM) and the filtrate was dried over Na2SO4. The solvent was removed under reduced pressure obtaining the product as a colorless oil (90 mg, 91% yield). 1H NMR (400 MHz, CDCl3) δ 9.67 – 9.56 (m, 2H), 2.41 – 2.28 (m, 1H), 2.11 – 1.97 (m, 2H), 1.75 – 1.62 (m, 2H), 1.51 – 1.40 (m, 1H), 1.32 – 1.19 (m, 1H), 1.11 (d, J = 7.1 Hz, 3H), 0.99 – 0.93 (m, 6H). 13C NMR (101 MHz, CDCl3) δ 205.3, 204.6, 58.3, 46.4, 28.5, 28.3, 23.1, 20.2, 19.7, 13.4. HRMS (ESI/TOF) m/z: [M + H]+ Calcd. for C10H19O2: 171.1380; found 171.1375. FT-IR (neat)  (cm-1) 1719. Synthesis of bis-allyl ether 13 Trans-menthene-diol (550 mg, 3.19 mmol) and allyl bromide (1.93 g, 16 mmol) were stirred in dry DMF (11 ml) at 0 °C under Ar. Then sodium hydride (639 mg (60% wt dispersion in mineral oil, 16 mmol) was added in small portions. The reaction mixture was stirred for 18 h at room temperature. Water was carefully added and the product isolated by extraction using diethyl ether. The solvent was removed under reduced pressure and the residue was purified via column chromatography (hexane:ethyl acetate, 99:1 v/v), obtaining the product as a colorless oil (788 mg, 98% yield). 1H NMR (400 MHz, CDCl3) δ 5.99 – 5.82 (m, 2H), 5.30 – 5.22 (m, 2H), 5.19 – 5.09 (m, 2H), 4.10 – 3.89 (m, 4H), 3.64 – 3.59 (m, 1H), 3.38 (t, J = 3.2 Hz, 1H), 1.88 – 1.76 (m, 1H), 1.70 – 1.59 (m, 1H), 1.56 – 1.53 (m, 1H), 1.37 – 1.23 (m, 4H), 0.95 – 0.88 (m, 9H). 13C NMR (101 MHz, CDCl3) δ 135.8, 135.7, 116.3, 116.1, 78.1, 75.9, 71.8, 70.8, 42.3, 30.6, 28.6, 26.9, 24.1, 21.1, 21.0, 18.0. HRMS (ESI/TOF) m/z: [M + Na]+ Calcd. for C16H28NaO2: 275.1982; found 275.1988. FT-IR (neat)  (cm-1) 3080, 1647. Synthesis of cyclic sulfite 14 To a stirred solution of the menthene diol (410 mg, 2.38 mmol) in DCM (7 mL) under argon was added triethylamine (530 mg, 5.24 mmol), followed by dropwise addition of thionyl chloride (340 mg, 2.86 mmol) in DCM (3 mL) at 0 °C. The reaction mixture was stirred at room temperature for 5 h. Then water was added, the mixture was filtered and washed with water and extracted with DCM. The combined organic phases were washed with HCl (1 M), NH4Cl (saturated solution) and dried over Na2SO4 The solvent was removed under reduced pressure and the residue was purified via column chromatography (hexane:ethyl acetate, 95:5 v/v), obtaining the product as a colorless oil (476 mg, 92% yield). 1H NMR (400 MHz, CDCl3) δ 4.74 – 4.66 (m, 1H), 4.25 – 4.15 (m, 1H), 2.72 – 2.51 (m, 1H), 2.15 – 1.41 (m, 5H), 1.37 – 1.20 (m, 1H), 1.16 – 0.98 (m, 6H), 0.97 – 0.90 (m, 3H). 13C NMR (101 MHz, CDCl3) δ 84.01, 83.52, 77.69, 44.58, 44.03, 31.39, 30.93, 30.82, 26.03, 25.55, 25.17, 24.98, 23.17, 22.99, 22.47, 22.09, 21.85, 21.70, 11.09, 11.06. HRMS (ESI/TOF) m/z: [M + Na]+ Calcd. for C10H18NaO3S: 241.0869; found 241.0876. FT-IR (neat)  (cm1) 1461, 1208, 1006, 756. S32 0200 400 600 0 50 100 Mass (%) T (°C) T5%= 225 °C Figure S4. TGA analysis of PMC (entry 9, Table 1). -100 0 100 200 -2 -1 0 1 2 Heat flow (mW) T [°C] Tg= 133 °C Figure S5. DSC analysis of PMC (entry 9, Table 1). S33 Mn (g/mol) Mw (g/mol) Mz (g/mol) Mp (g/mol) Ð 7.0043e3 8.5409e3 1.0146e4 8.8487e3 1.2194e0 Figure S6. GPC analysis of PMC (entry 9, Table 1) 0200 400 600 0 50 100 Mass (%) T (°C) T5%= 275 °C Figure S7. TGA analysis of PMC (entry 19, Table 1). S34 -100 0 100 200 -1 0 1 Heat flow (mW) T (°C) Tg= 121°C Figure S8. TGA analysis of PMC (entry 19, Table 1) Mn (g/mol) Mw (g/mol) Mz (g/mol) Mp (g/mol) Ð 5.9223e3 1.0442e4 1.5815e4 1.0321e4 1.7632e0 Figure S9. GPC analysis of PMC (entry 19, Table 1). S35 Analytical data for MC: Figure S10. 1H NMR spectrum (CDCl3, 400 MHz) of MC (dr > 20:1). Figure S11. 13C NMR spectrum (CDCl3, 101 MHz) of MC (dr > 20:1). a b + c a + b a + b S36 Figure S12. IR spectrum of MC (dr > 20:1). Figure S13. Molecular structure of MC (dr > 20:1). More details can be found in CCDC-2455347. S37 Analytical data for compound 1 Figure S14. 1H NMR spectrum (CDCl3, 400 MHz) of compound 1. Figure S15. 13C NMR spectrum (CDCl3, 101 MHz) of compound 1. b a a + b S38 Figure S16. IR spectrum (neat) of compound 1. S39 Analytical data for compound 2 Figure S17. 1H NMR spectrum (CDCl3, 400 MHz) of compound 2. Figure S18. 13C NMR spectrum (CDCl3, 101 MHz) of compound 2. b + c a a + b S40 Figure S19. IR spectrum (neat) of compound 2. S41 Analytical data for compound 3 Figure S20. 1H NMR spectrum (CDCl3, 400 MHz) of compound 3. Figure S21. 13C NMR spectrum (CDCl3, 101 MHz) of compound 3. a b a + b S48 -100 0 100 200 -2 -1 0 1 Heat flow (mW) T (°C) Tg= 141 °C Figure S31. DSC analysis of compound 6. 0200 400 600 0 50 100 Mass (%) T (°C) T5%= 275 °C Figure S32. TGA analysis of compound 6. S49 Mn (g/mol) Mw (g/mol) Mz (g/mol) Mp (g/mol) Ð 3.5568e3 3.8866e3 4.2338e3 3.8518e3 1.0927e0 Figure S33. GPC analysis of compound 6. S50 Analytical data for compound 7 Figure S34. 1H NMR spectrum (CDCl3, 400 MHz) of compound 7. Figure S35. 13C NMR spectrum (CDCl3, 101 MHz) of compound 7. a + b e c d a b c d S51 Figure S36. IR spectrum (neat) of compound 7. S52 Analytical data for compound 8 Figure S37. 1H NMR spectrum (CDCl3, 400 MHz) of compound 8. Figure S38. 13C NMR spectrum (CDCl3, 101 MHz) of compound 8. a + b d c a b c S53 Figure S39. IR spectrum (neat) of compound 8. S54 Analytical data for compound 9 Figure S40. 1H NMR spectrum (CDCl3, 500 MHz) of compound 9. Figure S41. 13C NMR spectrum (CDCl3, 126 MHz) of compound 9. a + b d + e c a b c+d e+f S55 Figure S42. IR spectrum (neat) of compound 9. S56 Analytical data for compound 10 Figure S43. 1H NMR spectrum (CDCl3, 400 MHz) of compound 10. Figure S44. 13C NMR spectrum (CDCl3, 101 MHz) of compound 10. a + b + c a + b S57 Figure S45. IR spectrum of compound 10. S64 Analytical data for compound 15 Figure S55. 1H NMR spectrum (CDCl3, 400 MHz) of compound 15. Figure S56. 13C NMR spectrum (CDCl3, 101 MHz) of compound 15. a + b a + b S65 Figure S57. IR spectrum of compound 15. S66 Analytical data for compound 16 Figure S58. 1H NMR spectrum (CDCl3, 400 MHz) of compound 16. Figure S59. 13C NMR spectrum (CDCl3, 101 MHz) of compound 16. a + b a + b S67 Figure S60. IR spectrum of compound 16. S68 Analytical data for compound 17 Figure S61. 1H NMR spectrum (CDCl3, 400 MHz) of compound 17. Figure S62. 13C NMR spectrum (CDCl3, 101 MHz) of compound 17. b a a S69 Figure S63. IR spectrum of compound 17. S70 Analytical data for compound 18 Figure S64. 1H NMR spectrum (CDCl3, 400 MHz) of compound 18. Figure S65. 13C NMR spectrum (CDCl3, 101 MHz) of compound 18. a + b c + d a+b a+b S71 Figure S66. IR spectrum of compound 18. S72 Analytical data for compound 19 Figure S67. 1H NMR spectrum (CDCl3, 400 MHz) of compound 19. Figure S68. 13C NMR spectrum (CDCl3, 101 MHz) of compound 19. b a b b a a c+d S73 Figure S69. IR spectrum of compound 19. S80 Analytical data for compound 23 Figure S79. 1H NMR spectrum (CDCl3, 400 MHz) of compound 23. Figure S80. 13C NMR spectrum (CDCl3, 101 MHz) of compound 23. e + f + g + h c + d a + b + i + m a+b c+d e+f S81 Figure S81. IR spectrum of compound 23. S82 9. References [1] T. Senthamarai, E. Lanaro, J. Tinker, A. Buchard, A. W. Kleij, Polym. Chem. 2025, 16, 2784-2790. [2] C. J. Whiteoak, N. Kielland, V. Laserna, E. C. Escudero-Adán, E. Martin, A. W. Kleij, J. Am. Chem. Soc. 2013, 135, 1228–1231. [3] T. Kiguchi, Y. Tsurusaki, S. Yamada, M. Aso, M. Tanaka, K. Sakai, H. Suemune, Chem. Pharm. Bull. 2000, 48, 1536-1540. [4] A. Wambach, S. Agarwal, A. Greiner, ACS Sustainable Chem. Eng. 2020, 8, 14690–14693. [5] L. Peña-Carrodeguas, C. Martín, A. W. Kleij, Macromolecules 2017, 50, 5337-5345. [6] M. Szewczyk, M. Magre, V. Zubar, M. Rueping, ACS Catal. 2019, 9, 11634−11639. [7] C. J. Whiteoak, N. Kielland, V. Laserna, E. C. Escudero-Adán, E. Martin, A. W. Kleij, J. Am. Chem. Soc. 2013, 135, 1228-1231.