Table 4.

Utilization of 4,5‐octanediol from the enzymatic cascades as substrate for the synthesis of 4,5‐dipropyl‐1,3‐dioxolane.

Entry[a]	Substrate [x mmol]	Formic acid [mL]	Product ratio SS/meso	Yield acetals[d] [%]
1	4,5‐octanediol >99 % meso (1.4)	0.3	0 : 100	11
2	4,5‐octanediol 93 % meso (1.4)	0.3	34 : 66	13
3	4,5‐octanediol >99 % S,S (1.4)	0.3	100:0	18
4[b]	4,5‐octanediol >99 % S,S (1.4)	2×0.3	100:0	31
5[c]	4,5‐octanediol (1.3) without purification 89 % meso	0.3	40 : 60	10

[a] Ru(triphos)(tmm) (0.003 mmol), Bi(OTf)₃ (0.032 mmol), formic acid (0.3 mL), CPME (2 mL) 90 °C, 16 h, H₂ (100 bar). [b] Reloaded with formic acid (0.3 mL), Ru(triphos)(tmm) (0.0025 mmol), Bi(OTf)₃ (0.017 mmol), CPME (1 mL) after 16 h, 32 h reaction time. [c] 4,5‐Octanediol (89 % meso), butyroin (1.4 mmol). [d] TON and yield were determined by ¹H NMR spectroscopy using mesitylene as internal standard.