(R)-tert-butyl 1-aminopropan-2-ylcarbamate

We report the catalytic hydroamination of amino acid esters with carbodiimides and isocyanates to furnish corresponding quinazolinone and urea derivatives under mild conditions using two titanium(iv) complexes [(ImRN)2Ti(NMe2)2] (R = tBu, 2a; R = Mes, 2b), which were synthesised by reacting tetrakis(dimethylamido)titanium(iv) [Ti(NMe2)4] with imidazolin-2-imine [ImRNH; R = tert-butyl (tBu) (1a), mesityl (Mes) (1b)] in a 1 : 2 molar ratio in toluene. Furthermore, the reaction of titanium complex 2a with 2,6-diisopropylphenylamine (DippNH2) resulted in the corresponding mixed ligand titanium complex [κ1-(ImtBuN)2Ti(NMe2)(HNDipp)] (3a). In contrast, the reaction of complex 2a with 2,6-dimethyl phenol afforded the mono-imidazolin-2-iminato TiIV phenolate complex [κ1-(ImtBuN)Ti(O-1,6-Me2C6H3)3] (4a). The solid-state structures of complexes 2b, 3a, and 4a, established by single crystal X-ray diffraction analyses, confirmed a very short bond between titanium and imidazolin-2-iminato nitrogen in each case. Titanium complexes 2a and 2b exhibited relatively high conversion, superior selectivity and broad functional group tolerance in both hydroamination reactions under mild conditions. We propose the most plausible mechanism for the guanylation/cyclisation of amino acid esters to carbodiimides on the basis of a number of controlled reactions.

Complex (PNP)Nb(CH3)2(OAr) (PNP = N[2-P(i)Pr2-4-methylphenyl]2(-), Ar = 2,6-(i)Pr2C6H3), prepared from treatment of (PNP)NbCl3 with NaOAr followed by 2 equiv of H3CMgCl, can be oxidized with [FeCp2][OTf] to afford (PNP)Nb(CH3)2(OAr)(OTf). While photolysis of the latter resulted in formation of a rare example of a niobium methylidene, (PNP)Nb═CH2(OAr)(OTf), treatment of the dimethyl triflate precursor with the ylide H2CPPh3 produced the mononuclear group 5 methylidyne complex, (PNP)Nb≡CH(OAr). Adding a Brønsted base to (PNP)Nb═CH2(OAr)(OTf) also resulted in formation of the methylidyne. Solid-state structural analysis confirms both methylidene and methylidyne moieties to be terminal, having very short Nb-C distances of 1.963(2) and 1.820(2) Å, respectively. It is also shown that methylidyne for nitride cross-metathesis between (PNP)Nb≡CH(OAr) and NCR (R = tert-butyl or 1-adamantyl) results in formation of a neutral and mononuclear niobium nitride, (PNP)Nb≡N(OAr), along with the terminal alkyne HC≡CR.

The title compound, C(14)H(30)N(2)O(2)S(2), is the product of the monoaddition reaction of tert-butyl magnesium chloride with bis-[(R)-N-tert-butanesulfinyl]ethanediimine. There are two almost identical mol-ecules in the asymmetric unit, the mol-ecular conformation of which is stabilized by an intra-molecular N-H⋯N hydrogen bond.