We report the syntheses of 1,4-diazacycles by diol-diamine coupling, uniquely made possible with a (pyridyl)phosphine-ligated ruthenium(II) catalyst (1). The reactions can exploit either two sequential N-alkylations or an intermediate tautomerization pathway to yield piperazines and diazepanes; diazepanes are generally inaccessible by catalytic routes. Our conditions tolerate different amines and alcohols that are relevant to key medicinal platforms. We show the syntheses of the drugs cyclizine and homochlorcyclizine in 91% and 67% yields, respectively.