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This review outlines recent advances in Brønsted acid-catalysed dehydrative replacement reactions for C-C, C-O, C-N and C-S bond development. The wide range of processes which are today accessible using simple alcohols once the formal electrophile are highlighted, while existing limitations and consequently possible future directions for research will also be discussed.In the budding yeast Saccharomyces cerevisiae, Svl3 and Pam1