Titanium(IV) isopropoxide and ethylmagnesium bromide catalyzed reaction of 2-alkynylamines with Et2Zn, followed by deuterolysis/hydrolysis and iodinolysis, affords substituted (Z)-pent-2-en-2,5-d 2-1-amines, (Z)-pent-2-en-1-amines (65–88%), and substituted (Z)-2,5-diiodopent-2-en-1-amines (55–63%). It is suggested that the reaction proceeds through the formation of cyclic organotitanium derivatives. The reaction between 1-alkynylphosphines and Et2Zn in the presence of catalytic amounts of Ti(O-iPr)4 and EtMgBr leads to trisubstituted 1-alkenylphosphine oxides with high regioselectivity and stereoselectivity.

The EtMgBr and Ti(O-iPr)4-catalyzed ethylzincation of 1-alkynylphosphine sulfides with Et2Zn in diethyl ether followed by hydrolysis and deuterolysis affords corresponding β,β-disubstituted 1-alkenylphosphine sulfides with high yield. The EtMgBr and Ti(O-iPr)4-catalyzed reaction of 2-alkynylamines, 1-alkynylphosphines, and 1-alkenylphosphine sulfides with Et2Zn in various solvents was studied. It has been found that the reaction of 2-alkynylamines and 1-alkynylphosphines in methylene chloride, hexane, toluene, benzene, and anisole leads to the selective formation of 2-alkenylamines and 1-alkenylphosphine oxides after oxidation with H2O2.

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