Formation of enediynes by reductive coupling followed by alkyne metathesis
AssigneeMassachusetts Institute of Technology
InventorsChristopher C. Cummins, James M. Blackwell
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Abstract
One aspect of the present invention relates to methods of preparing enedialkylidyne complexes, enediynes, and alkyne metathesis catalysts, as well as methods of catalyzing alkyne metathesis reactions. The present invention also relates to methods of activating enedialkylidyne complexes for metathesis. The present invention also relates to enedialkylidyne complexes.
Claims55
A method of preparing an enedialkylidyne complex, comprising:
- (a) combining a terminal alkyne with a first transition metal complex to give a second transition metal complex;
- and
- (b) treating the second transition metal complex with a base.
A method of preparing an enediyne or an alkyne metathesis catalyst or both, comprising the step of reacting an alkyne with an enedialkylidyne complex, thereby forming an enediyne or an alkyne metathesis catalyst or both.
A method of catalyzing an alkyne metathesis reaction, comprising combining an alkyne with an enedialkylidyne represented by formula V or VI:
- wherein, independently for each occurrence:
- M is a Group V, VI, VII, or VIII transition metal;
- X is a σ-bonded ligand:
- L is a donor bonded ligand;
- R1, R2, R3, and R4 are H, or optionally substituted alkyl, aryl, or aralkyl;
- or R1 and R2 are covalently bonded to each other to form a 4-20 membered ring;
- a is an integer from 1 to 3 inclusive;
- and
- b is an integer from 0 to 4 inclusive.
A method of activating an enedialkylidyne complex for metathesis, wherein the endedialkylidyne complex comprises at least one σ-bonded amine ligand, comprising reacting the enedialkylidine complex with an alcohol to form at least one σ-bonded alkoxy ligand.
An enedialkylidyne complex having formula VIII, IX, or X:
- wherein, independently for each occurrence:
- M is a Group VI transition metal;
- X is a σ-bonded ligand;
- R1 and R2 are an optionally substituted alkyl, aryl, or aralkyl;
- or R1 and R2 are covalently bonded to each other to form a 4-20 membered ring;
- and
- R3 is H, or optionally substituted alkyl, aryl, or aralkyl.
Dependencies are inferred from the claim text.