Intermediates for and synthesis of 3-methylene cephams

A process of preparing compounds of the formula I:

• said process comprising the step of reacting a compound of the formula II;
• MEx(H2O)y (III)
• with a catalyst of the formula III in an inert solvent;
• wherein:
• M is Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Zr, Hf, Th, Nb, Ta, U, Bi, or In;
• E is O[SO2(C1-C6 polyfluoroalkyl)], N[SO2(C1-C6 polyfluoroalkyl)]2, or C[SO2(C1-C6 polyfluoroalkyl)]3;
• x is 3 or when M is Th then x is 4;
• y is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9;
• R is a carboxylic acid protecting group;
• R′ is hydrogen or a carboxylic acid protecting group;
• R1 is a group of the formula;
• R2 is C2-C4 alkenylene, C2-C4 alkylene, 1,2-phenylene, or 1,2-cyclohexenylene;
• R2′ is C1-C3 alkyl, C1-C6 haloalkyl, C1-C3 alkoxy, or 2,2,2-trichloroethoxy;
• R3 is hydrogen, C1-C3 alkyl, halomethyl, cyanomethyl, 3-(2-chlorophenyl)-5-methylisoxazol-4-yl, benzyloxy, 4-nitrobenzyloxy, 2,2,2-trichloroethoxy, tert-butoxy, 4-methoxybenzyloxy, phenyl, substituted phenyl, a group of the formula R0—(Q)m—CH2—, a heteroarylmethyl group of the formula R″CH2—, or a group of the formula
• R0 is phenyl, substituted phenyl, 2-thienyl, 3-thienyl, or 1,4-cyclohexyldienyl;
• R″ is 2-furyl, 3-furyl, 2-thiazolyl, or 5-isoxazolyl;
• m is 0 or 1,
• Q is O or S;
• W is protected hydroxy, or protected amino;
• Y is hydrogen, acetyl, or nitroso;
• X is chloro, bromo, —OR4, —SR5, or —NR6R7 wherein:
• (a) R6 is hydrogen and R7 is hydrogen, phenyl, substituted phenyl, or —NHR8;
• or wherein (b) R6 is —COOR9 or —COR9 and R7 is —NH—COOR9 or —NH—COR9;
• or wherein (c) R6, R7, and the nitrogen to which each is attached combine to form an imido group of the formula
• R4 is hydrogen, C1-C10 alkyl, (C1-C3 alkyl)aryl, C1-C6 haloalkyl, or —COR10;
• R5 is C1-C6 alkyl, phenyl, substituted phenyl, phenyl(C1-C3 alkyl), or substituted phenyl(C1-C3 alkyl);
• R8 is aminocarbonyl, C1-C3 alkylaminocarbonyl, C1-C3 alkoxycarbonyl, C1-C3 alkylcarbonyl, or tosyl;
• R9 is C1-C6 alkyl, or phenyl;
• R10 is C1-C6 alkyl, C1-C6 polyfluoroalkyl, C3-C6 cycloalkyl, adamantyl, phenyl, substituted phenyl, (C1-C3 alkyl)phenyl, or substituted phenyl(C1-C3 alkyl), or a group of the formula
• Z is solid polymer support;
• and
• Z1 is one or two groups independently selected from the group consisting of hydrogen, halo, hydroxy, protected hydroxy, nitro, cyano, trifluoromethyl, C1-C4 alkyl, and C1-C4 alkoxy.