The initial synthesis of annulated steroidal pyrimidines by the groups of Clinton (Ackerman et al., 1964) and Ruggieri (De Ruggieri and Gandolfi, 1965; De Ruggieri et al., 1965, 1966a,b) dates back to the mid-1960s. Their synthetic approach was based on condensation of guanidines with activated α,β-unsaturated ketones, primarily β-enol ethers, and have become widely applied in chemistry of steroids due to a great diversity of obtainable products (Romo et al., 1968; Bajwa and Sykes, 1978; Hajos and Snatzke, 1989; Mallamo et al., 1992; Hasan et al., 1995; Forgo and Vincze, 2002). Unfortunately, this method suffers from drawbacks, such as harsh reaction conditions, moderate yields and high labor content/cost of preparing starting materials. Therefore, over the years a considerable effort has been directed toward the development of alternative methods for steroidal pyrimidines synthesis. Improved solid phase protocol of β-enol ethers heterocyclization was elaborated toward synthesis of steroidal A-ring fused pyrimidines (Barthakur et al., 2009). Although there is an example of condensation using β-enamino ketones (Xu et al., 2012). Boruah group have developed a range of methods, among which are three-component condensation of steroidal ketones with aromatic aldehydes and amidine derivatives in presence of potassium tert-butoxide (Saikia et al., 2014), Pd(OAc)2-catalyzed hetrocyclization of steroidal β-halo-α,β-unsaturated aldehydes with amidines (Gogoi et al., 2013) and SmCl3-catalyzed condensation of β-formyl enamide with urea under microwave irradiation (Barthakur et al., 2007). Baran group reported synthesis of 4,5-disubstituted pyrimidines from steroidal ketones and formamidine acetate (Baran et al., 2006). Here we have achieved high-yielding syntheses of novel A- and D-rings annulated steroidal pyrimidines via developed by us metal-free condensations of β-chlorovinyl aldehydes with amidines (Komendantova et al., 2017). These reactions are efficiently occur under mild conditions, with the added advantage that heterocyclization pattern can be easily switch to steroidal dihydrotriazines, previously unexplored class of heterosteroids.