Reduction of (6R)-6-amino-6, 7-dihydro-2-thienyl-1, 4-thiazepin-5 (4H)-one derivatives with Mg–MeOH gave the corresponding perhydrothiazepinones. Protection with trityl group at the 6-amino group gave predominantly the 2S, 6R isomer which was converted to the potent angiotensin-converting enzyme (ACE) inhibitor. The ACE inhibitor having the 6, 7-dihydro-l, 4-thiazepin-5 (4H)-one ring was also prepared.