4-Yn-1-ols bearing a terminal triple bond undergo oxidative cyclization–alkoxycarbonylation in methanol at 70°C and 100 atm of a 9:1 mixture of carbon monoxide and air in the presence of catalytic amounts of [PdI4]2 in conjunction with an excess of KI to give 2E-[(methoxycarbonyl)methylene]tetrahydrofurans in good yields. A competing reaction, cycloisomerization–hydromethoxylation leading to 2-methoxy-2-methyltetrahydrofurans, can be easily curtailed by increasing the KI excess. The latter products can be prepared from 4-yn-1-ols and methanol in high yields using the same catalytic system and without KI excess in the absence of carbon monoxide.
PALLADIUM-CATALYZED SYNTHESIS OF 2E-[(METHOXYCARBONYL)METHYLENE]TETRAHYDROFURANS: OXIDATIVE CYCLIZATION-METHOXYCARBONYLATION OF 4-YN-1-OLS VERSUS CYCLOISOMERIZATION-HYDROMETHOXYLATION
GABRIELE, Bartolo;
2000-01-01
Abstract
4-Yn-1-ols bearing a terminal triple bond undergo oxidative cyclization–alkoxycarbonylation in methanol at 70°C and 100 atm of a 9:1 mixture of carbon monoxide and air in the presence of catalytic amounts of [PdI4]2 in conjunction with an excess of KI to give 2E-[(methoxycarbonyl)methylene]tetrahydrofurans in good yields. A competing reaction, cycloisomerization–hydromethoxylation leading to 2-methoxy-2-methyltetrahydrofurans, can be easily curtailed by increasing the KI excess. The latter products can be prepared from 4-yn-1-ols and methanol in high yields using the same catalytic system and without KI excess in the absence of carbon monoxide.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
