Valuable enantiopure alcohols are widely found in nature. Considering the impressive catalyst control observed with phenethyl alcohol (2b) using our method, we decided to investigate more complex substrates (Scheme 3). We first reoptimized the reaction for the use of the alcohol as limiting reagent (See SI for more information). The use of 1 equiv of (-)-menthol (5a) gave alkyne 6 in 81% yield and excellent diastereoselectivity (2:98 dr) after overnight reaction. When (+)-menthol (5b) was submitted to the same conditions, product 7 was obtained in 89% yield and 96:4 dr, displaying again an excellent catalyst control. Other terpene derived alcohols could also be used, giving products 8-10 in 64-89% yield and 85:15-97:3 dr. A lower selectivity was observed when starting from the chiral tertiary alcohol cedrol (5d) (product 9, 85:15 dr). The reaction was also successful for a protected serine derivative 5f as an example of chiral primary alcohol, and ether 11a was obtained in 63% yield and 93:7 dr. The reaction of alcohol 5f was also performed with TIPS-substituted reagent 2d, giving compound 11b in 66% yield and 90:10 dr. Compound 11b was obtained in slightly higher yield and diastereoselectivity at the 1 mmol scale.