ALLYLSTANNATION .6. ALLYLATION AND ALLENYLATION OF ALDEHYDES AND KETONES BY ALLYL-TIN AND ALLENYL-TIN CHLORIDES IN THE PRESENCE OF WATER

Allyl- and propargyl-carbinols can be readily prepared in one pot reaction, in the presence of water, by addition of allyl- or allenyl-tin chlorides to carbonyl compounds. The reactions of Bu3-n(CH2CHCH2)SnCln, Bu3-n(CH3CHCHCH2)SnCln (n = 1, 2) and Bu2(CH2CCH)SnCl and the carbonyl compounds RCHO (R = H, C2H5, (CH3)2CH, (CH3)3C, (E)-CH3CHCH, C6H5) and RCOR′ (R = R′ = CH3 and R = CH3 and R′ = (CH3)2CH) have been examined. The monochloroorganotin derivatives undergo the following quantitatvive reactions: Bu2(CH2CHCH2)SnCl + RCOR′ + 12H2O → R(HO)C(R′)CH2CHCH2 + 12[Bu2SnCl]2O↓ (1) Bu2(CH2CHCH2)SnCl + RCOR′ + 12H2O → R(HO)C(R′)CH2CHCH + 12[Bu2SnCl]2O↓ (2) Reaction (2), which involves the allenic substrate, is characterized by rearrangement of the unsaturated chain, the propargylic carbinol being isolated as the major product (∼ 90%).