[a], [b] 2 mol % of DBTO was used as a catalyst for polymerization, transesterification was done at 120 °C and polycondensation was performed at hypothesized that if the reactive hydroxyl functional groups and the core of the multicyclic pinene ring are connected by a short extended chain, then the bicyclic rings will not be opened during polymerization -or embedded in the polymer chain -but can rather protrude from the backbone. Such spatial arrangement may also open up the doors to H-bonding between the core and the ester unit that can stabilize the molecule in a particular stereoisomeric form. To synthesize chiral diols from (-)-α-pinene that are not prone to undergo ring opening during polymerization, we envisioned a concise retro-synthetic plan for the synthesis of a novel (-)-α-pinene-based chiral diol from (R)-(-)-nopol (1) via hydroboration followed by oxidation. (R)-(-)-nopol (1) is a commercially available natural product that can easily be synthesized from α-pinene. (R)-(-)-nopol (1) on hydroboration followed by oxidation using H2O2 afforded the expected transhydroxy nopol (2, abbreviated as HN) as a highly viscous colorless liquid in 90% of yield (Scheme 1). The structure of the diol HN (2) was confirmed by 1D, 2D NMR, and IR spectroscopy, and the higher coupling constant (J) value between the protons attached to carbon 2 and 3 suggests that they are trans to each other (see the supporting information (SI), Figure ) which was also further confirmed by 1H COSY. All the diastereotropic protons were observed as two peaks at two different regions (2',2'', 4, 7). After having the required unsymmetrical chiral αpinene-based diol (2) in hand, we demonstrated the copolymerization of the same with a series of bio-based aromatic (6) and aliphatic diesters (7, 8, 9) via transesterification followed by polycondensation under solvent-free conditions in the presence of DBTO as a catalyst. All the diesters reacted smoothly with the diol (HN, 2) and resulted in moderate to excellent yields of the polyesters (HN_FDCA (10), HN_DMS (11), HN_DMA (12), HN_DMSc ( )). Also, to understand the effect of the chain length of the diol on the physical, chemical, and thermal behavior of the resulting polyesters, we have synthesized another (-)-α-pinenebased chiral diol (5) from (R)-(-)-myrtenal (3) or (R)-(-)-myrtenol (4) on a preparative scale (Scheme 2). (R)-(-)-myrtenal (3) and (R)-(-)-myrtenol ( ) are also natural products, inexpensive commercially available compounds, and their valorization afforded the chiral α-pinene-based diol (5) on hydroboration followed by oxidation as a colorless crystalline solid in 85% yield (structure confirmed by 1D, 2D NMR, and IR spectroscopy). The trans stereochemistry and the diasteriotropic protons (2', 4, 7)