Six-membered
The present invention provides a catalyst complex or ligand, and compositions thereof, for use in a variety of organic reactions having high reactivity and enantioselectivity. The catalyst is a N-heterocyclic carbene having three fused rings with first and second rings being six-membered rings and the third being a five-membered ring. The first ring is fused to the second and has four substituents. The second ring has two nitrogens flanking a carbene atom with one nitrogen bound to a substituent. The carbene atom may optionally be bonded to a metal. The third ring is fused to the second ring and contains two nitrogens. The third ring of the catalyst has a double bond and two substituents on adjacent non-fused carbons. A non-fused nitrogen of the third ring is partially bonded to another substituent. Methods for the synthesis and use of the catalyst embodiments of the present invention are also provided.
1. A method comprising the step of reacting a substrate in a β-functionalization reaction in the presence of a catalyst to produce a product,
wherein the substrate is a molecule having a double bond between two carbon atoms,
wherein one of those carbons is bonded to an electron withdrawing group (EWG) and the other carbon is bonded to a variable substituent or group,
wherein the product of the β-functionalization reaction has an enantiomeric excess of about 75% or greater, and
wherein the catalyst has the following structural formula:
wherein each R 1 group bound to the third ring is one of the following: alkyl, vinyl, allyl, alkynyl or aryl,
wherein the R 2 group bound to the second ring is one of the following: alkyl, vinyl, allyl, alkynyl or aryl, and
wherein the carbon atom positioned between the nitrogens of the second ring and bonded to Cu is a carbene atom.
2. The method of claim 1 , wherein each R 1 group is aryl.
3. The method of claim 2 , wherein each R 1 group is phenyl.
4. The method of claim 1 , wherein R 2 is aryl.
5. The method of claim 4 , wherein R 2 is a radical group having the following formula:
wherein each of the radical groups R 3 , R 4 , and R 5 are alkyl.
6. The method of claim 5 , wherein two members of the group consisting of R 3 , R 4 and R 5 are the same and the third member of the group is different from the two members of the group that are the same.
7. The method of claim 6 , wherein R 3 and R 5 are each methyl.
8. The method of claim 5 , wherein R 3 , R 4 and R 6 are different from each other.
9. The method of claim 5 , further comprising the step of isolating or purifying the product of the reacting step.
10. The method of claim 5 , further comprising the step of measuring the product of the reacting step.