Photoadditions of phenylacetates to phthalimide in pH 7 buffer solution give the corresponding benzylated-hydroxyphthalimidines in moderate to high yields of up to 94%. In a micro-structured reactor, higher conversions and purities are achieved. With branched phenylacetates, photoaddition affords diastereoisomeric mixtures with low to moderate de values. Subsequent acid-catalyzed dehydration furnishes the corresponding 3- ...