Recent years have witnessed increasing interest in the synthesis of low-sym
metry single phthalocyanines (Pcs) since they may show, among other applica
tions and advantages, interesting second-order nonlinear optical (NLO) prop
erties, This potential of unsymmetrically substituted and regioisomerically
pure phthalocyanines has motivated researchers in this field to develop se
lective methods for synthesizing macrocycles of this type. In this microrev
iew, we focus on the approaches reported by other research groups as well a
s ourselves that allow the predominant or exclusive formation of the requir
ed compounds. The selective preparation of differently substituted or intri
nsically unsymmetrical Pc-related systems and Pc homologues is also discuss
ed.