(+)-3-Carene based chiral phosphites represent an important type of chirality transfer agents for asymmetric catalysis [1,2]. The most important advantages of phosphite-type ligands include their pronounced π-acidity, oxidation stability, as well as their synthetic availability and low cost. Herein we report the 31P NMR investigation of new synthesized [1] P*-chiral phosphites based on 3carene 1 as one of cheapest natural optically active monoterpene. The 31P NMR spectroscopic data for 2-3 are summarized in Table 1. Compound 2 with NEt2 exocyclic fragment is formed as single stereoisomer, while 3 contain 3% of the second epimer by P* - stereocentre. To estimate steric demands of chiral phosphites, we calculated their Tolman’s angles [3] by the reported method using of semiempirical quantum mechanical AM1 techniques with full optimization of geometrical parameters [4]. The obtained results show that the steric demands of 2,3 vary over a rather wide range between 90° and 122°.