4-Aryl-2-anilinopyrimidines and 2,4-dianilinopyrimidines are privileged structures found in many drug-like molecules and biologically active compounds. A method for the quick assembly of novel 4-aryl- and 4-anilino-2-(heteroarylamino)pyrimidines via Buchwald–Hartwig N-arylations at elevated temperatures under sealed tube conditions is reported. This method’s convenience and practicality is demonstrated through the preparation of several novel non-nucleoside reverse transcriptase inhibitor (NNRTI) analogues.