Biosynthesis of 2-Methylbutyl, 2-Methyl-2-butenyl, and 2-Methylbutanoate Esters in Red Delicious and Granny Smith Apples Using Deuterium-Labeled Substrates

Abstract

2-Methylbutanoate esters, especially ethyl 2-methylbutanoate, are key contributors to fruit aroma. The biosynthetic origins and interconversions of 2-methylbutyl and 2-methylbutanoate esters in Red Delicious and Granny Smith apples were determined by feeding deuterium-labeled substrates with GC−MS identification of the deuterated aroma volatiles produced. Deuterium-labeled isoleucine was fed to apple peel, and 2-methylbutanoic- d 3 acid, 2-methylbutanol- d 3, and ethyl 2-methylbutanoate- d 3 were fed as vapor to whole apples. An array of labeled 2-methylbutyl and 2-methylbutanoate esters was produced from each substrate with significant differences in products and product distributions between the two apple cultivars. Novel 2-methyl-(2 E )-butenyl esters were identified as biosynthetic products in the aroma of Red Delicious but not Granny Smith apples. Keywords: Biosynthesis; apple; aroma volatiles; 2-methylbutyl; 2-methylbutanoate; 2-methyl-2-butenyl; deuterium