Catalytic compositions and methods for asymmetric allylic alkylation

A catalytic organometallic composition, effective to catalyze the enantioselective alkylation of an allyl group bearing a leaving group at an allylic position, wherein the composition is the product of a process which comprises:

• contacting with a chiral ligand L1, in a suitable solvent, a soluble complex of a metal selected from tungsten (0), chromium (0), and molybdenum(0), having ligands which form a stable complex with the metal and are displaceable by ligand L1 under the conditions of said contacting,
• wherein said ligand L1 comprises:
• a chiral component derived from a chiral diamine, said component comprising first and second carbon atoms, each bearing a binding group —NH—(C═O)—B, wherein
• said carbon atoms are connected by a direct bond or by a chain of one to three atoms comprising linkages selected from alkyl, alkyl ether, alkyl amino, and combinations thereof;
• each group B is selected from alkyl, cycloalkyl, heterocycle, aryl, and aralkyl;
• at least one group B is a N-heterocyclic or N-heteroaryl group CyN having an sp2 hybridized ring nitrogen atom effective to coordinate to said metal atom;
• and
• at least one of said carbon atoms is a chiral carbon atom bearing a further substituent, wherein said substituent or substituents are independently selected from aryl, aralkyl, carbocycle, heterocycle, and secondary or tertiary alkyl having 3 or more carbons, and where substituents on adjacent chiral carbon atoms may together form a ring;
• whereby said complex undergoes a ligand exchange reaction, such that chiral ligand L1 becomes coordinated to said metal atom.

A method of selective alkylation of an allyl group bearing a leaving group at an allylic position, said method comprising

• reacting a substrate containing said allyl group with an alkylating agent in the presence of a catalytic composition formed by contacting, in a suitable solvent, catalytic amounts of:
• (i) a chiral ligand L1, and (ii) a soluble complex of a metal selected from the group consisting of molybdenum (0), tungsten (0), and chromium (0), having ligands which form a stable complex with the metal and are displaceable by ligand L1 under the conditions of said contacting,
• under conditions effective to produce an alkylated substrate which is enriched in one of the possible isomeric products of such alkylation,
• wherein said chiral ligand L1 comprises:
• a chiral component derived from a chiral diamine, said component comprising first and second carbon atoms, each bearing a binding group —NH—(C═O)—B, wherein
• said carbon atoms are connected by a direct bond or by a chain of one to three atoms comprising linkages selected from alkyl, alkyl ether, alkyl amino, and combinations thereof;
• each group B is selected from alkyl, cycloalkyl, heterocycle, aryl, and aralkyl;
• at least one group B is a N-heterocyclic or N-heteroaryl group CyN having an sp2 hybridized ring nitrogen atom effective to coordinate to said metal atom;
• and
• at least one of said carbon atoms is a chiral carbon atom bearing a further substituent, wherein said substituent or substituents are independently selected from aryl, aralkyl, carbocycle, heterocycle, and secondary or tertiary alkyl having 3 or more carbons, and where substituents on adjacent chiral carbon atoms may together form a ring.