Polystyrene-supported palladacycle catalysts

A method for promoting a coupling reaction, comprising conducting the reaction in the presence of a palladacycle catalyst of formula (I)

• in which
• each is a single bond or a double bond, provided that if one is a double bond, its neighboring is not a double bond;
• each of X and Z, independently, is —P(R′)—, —S—, —N(R′)—, or —N═, in which R′ is alkyl, aryl, cyclyl, heteroaryl, or heterocyclyl;
• each of Y1 and Y2, independently, is an anion of an organic or inorganic acid;
• each of X1, X2, X3, Z1, Z2, and Z3, independently, is —C═, —CR″—, in which R″ is H, alkyl, aryl, cyclyl, heteroaryl, or heterocyclyl;
• and
• each of R1, R2, R3, R4, R5, R6, R7, and R8, independently, is H, alkyl, aryl, cyclyl, heteroaryl, or heterocyclyl, or X, R1, R2, and X1 together form a 3–8 membered ring, or X1, R2, R3, and X2 together form a 3–8 membered ring, or X2, R3, R4, and X3 together form a 3–8 membered ring, or Z, R5, R6, and Z1 together form a 3–8 membered ring, or Z1, R6, R7, and Z2 together form a 3–8 membered ring, or Z2, R7, R8, and Z3 together form a 3–8 membered ring;
• wherein at least one of R1, R2, R3, R4, R5, R6, R7, and R8, or the ring formed from R1, X, X1, and R2, or the ring formed from R2, X1, X2, and R3, or the ring formed from R3, X2, X3, and R4, or the ring formed from R5, Z, Z1, and R6, or the ring formed from R6, Z1, Z2, and R7, or the ring formed from R7, Z2, Z3, and R8 being connected to a first polymer.

A method for preparing a palladacycle catalyst of formula (I)

• in which
• each is a single bond or a double bond, provided that if one is a double bond, its neighboring is not a double bond;
• each of X and Z, independently, is —P(R′)—, —S—, —N(R′)—, or —N═, in which R′ is alkyl, aryl, cyclyl, heteroaryl, or heterocyclyl;
• each of Y1 and Y2 is an anion of an organic or inorganic acid;
• each of X1, X2, X3, Z1, Z2, and Z3, independently, is —C═, —CR″—, in which R″ is H, alkyl, aryl, cyclyl, heteroaryl, or heterocyclyl;
• and
• each of R1, R2, R3, R4, R5, R6, R7, and R8, independently, is H, alkyl, aryl, cyclyl, heteroaryl, or heterocyclyl, or X, R1, R2, and X1 together form a 3–8 membered ring, or X1, R2, R3, and X2 together form a 3–8 membered ring, or X2, R3, R4, and X3 together form a 3–8 membered ring, or Z, R5, R6, and Z1 together form a 3–8 membered ring, or Z1, R6, R7, and Z2 together form a 3–8 membered ring, or Z2, R7, R8, and Z3 together form a 3–8 membered ring;
• wherein at least one of R1, R2, R3, R4, R5, R6, R7, and R8, or the ring formed from R1, X, X1, and R2, or the ring formed from R2, X1, X2, and R3, or the ring formed from R3, X2, X3, and R4, or the ring formed from R5, Z, Z1, and R6, or the ring formed from R6, Z1, Z2, and R7, or the ring formed from R7, Z2, Z3, and R8 is connected to first polystyrene;
• the method comprising reacting styrene with a palladacycle compound of formula (I), in which
• each is a single bond or a double bond, provided that if one is a double bond, its neighboring is not a double bond;
• each of X and Z, independently, is —P(R′)—, —S—, —N(R′)—, or —N═, in which R′ is alkyl, aryl, cyclyl, heteroaryl, or heterocyclyl;
• each of Y1 and Y2 is an anion of an organic or inorganic acid;
• each of X1, X2, X3, Z1, Z2, and Z3, independently, is —C═, —CR″—, in which R″ is H, alkyl, aryl, cyclyl, heteroaryl, or heterocyclyl;
• and
• each of R1, R2, R3, R4, R5, R6, R7, and R8, independently, is H, alkyl, aryl, cyclyl, heteroaryl, or heterocyclyl, or X, R1, R2, and X1 together form a 3–8 membered ring, or X1, R2, R3, and X2 together form a 3–8 membered ring, or X2, R3, R4, and X3 together form a 3–8 membered ring, or Z, R5, R6, and Z1 together form a 3–8 membered ring, or Z1, R6, R7, and Z2 together form a 3–8 membered ring, or Z2, R7, R8, and Z3 together form a 3–8 membered ring;
• wherein one of R1, R2, R3, R4, R5, R6, R7, and R8, or the ring formed from R1, X, X1, and R2, or the ring formed from R2, X1, X2, and R3, or the ring formed from R3, X2, X3, and R4, or the ring formed from R5, Z, Z1, and R6, or the ring formed from R6, Z1, Z2, and R7, or the ring formed from R7, Z2, Z3, and R8 is connected to a first vinyl group.