Alkene isomerization as an entry to efficient alternating ring-opening metathesis polymerization (i-AROMP)

1. A process for producing an alternating AB copolymer comprising the repeating unit I,

comprising:

(1) optionally isomerizing a cyclobutene of structure III in the presence of an olefin metathesis catalyst to form a cyclobutene III′:

(2) polymerization of the cyclobutene III′ with a cyclohexene II:

in the presence of an olefin metathesis catalyst;

wherein R is selected from the group consisting of H, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 3 -C 8 cycloalkyl, heterocyclyl, aryl, aralkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 3 -C 6 cycloalkyloxy, aryloxy, heterocyclyloxy, C 1 -C 20 alkylamino, C 2 -C 20 alkenylamino, C 3 -C 8 cycloalkylamino, heterocyclylamino, or arylamino and may be substituted with up to three substituents selected from halo, CN, NO 2 , oxo, amino, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, or a heterocyclic group;

n is between 2 and 500;

each substituent R 1 through R 4 is independently selected from the group consisting of H, aldehyde, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 3 -C 6 cycloalkyl, aryl, heterocyclyl, C 1 -C 20 alkoxy, C 1 -C 20 acyloxy, C 2 -C 20 alkenyloxy, C 3 -C 6 cycloalkyloxy, aryloxy, heterocyclyloxy, C 1 -C 20 alkylamino, C 2 -C 20 alkenylamino, C 3 -C 8 cycloalkylamino, heterocyclylamino, arylamino, and halogen, and adjacent substitutions of R 1 -R 4 may be taken together to form a 5- to 7-membered ring which may be substituted with up to three substituents selected from halo, CN, NO 2 , oxo, amino, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, or a heterocyclic group;

and wherein R 5 and R 6 are taken together to form a 5- or 6-membered ring, which may contain up to two heteroatoms in the ring selected from O or N, and which may be unsubstituted or substituted with up to four substituents selected from halo, CN, NO 2 , oxo, amino, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, or a heterocyclic group.

2. The process according to claim 1 , wherein the alternating AB copolymer comprises the repeating unit Ia

wherein X is O or NH; and

R a is selected from the group consisting of H, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 3 -C 8 cycloalkyl, heterocyclyl, aryl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 3 -C 6 cycloalkyloxy, aryloxy, heterocyclyloxy, C 1 -C 20 alkylamino, C 2 -C 20 alkenylamino, C 3 -C 8 cycloalkylamino, heterocyclylamino, or arylamino and may be substituted with up to three substituents selected from halo, CN, NO 2 , oxo, amino, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, or a heterocyclic group.

3. The process according to claim 1 , wherein R 5 and R 6 are taken together to form a cyclohexyl ring, which may be substituted.

4. The process according to claim 1 , wherein the alternating AB copolymer comprises the repeating unit Ib

wherein

R b is selected from the group consisting of H, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 3 -C 8 cycloalkyl, heterocyclyl, aryl, aralkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 3 -C 6 cycloalkyloxy, aryloxy, heterocyclyloxy, C 1 -C 20 alkylamino, C 2 -C 20 alkenylamino, C 3 -C 8 cycloalkylamino, heterocyclylamino, or arylamino and may be substituted with up to three substituents selected from halo, CN, NO 2 , oxo, amino, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, or a heterocyclic group.

5. The process according to claim 1 , wherein the cyclohexene has the structure IIa:

wherein each substituent R 2 and R 3 is independently selected from H, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 3 -C 8 cycloalkyl, heterocyclyl, aryl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 3 -C 6 cycloalkyloxy, aryloxy, heterocyclyloxy, C 1 -C 20 alkylamino, C 2 -C 20 alkenylamino, C 3 -C 8 cycloalkylamino, heterocyclylamino, arylamino or halogen, and may be substituted with up to three substituents selected from halo, CN, NO 2 , oxo, amino, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, and a heterocyclic group, and alternatively R 2 and R 3 are be taken together to form a 5- to 7-membered ring which may be substituted with up to three substituents selected from halo, CN, NO 2 , oxo, amino, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, or a heterocyclic group.

6. The process according to claim 5 , wherein the cyclohexene has the structure:

7. The process according to claim 1 , wherein the cyclobutene has the structure IIIa or IIIa′, in which the cyclobutene of structure IIIa is isomerized to a cyclobutene of structure IIIa′

in the presence of an olefin metathesis catalyst,

wherein X is selected from O, or NH, and

R a is selected from the group consisting of H, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 3 -C 8 cycloalkyl, heterocyclyl, aryl, aralkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 3 -C 6 cycloalkyloxy, aryloxy, heterocyclyloxy, C 1 -C 20 alkylamino, C 2 -C 20 alkenylamino, C 3 -C 8 cycloalkylamino, heterocyclylamino, or arylamino and may be substituted with up to three substituents selected from halo, CN, NO 2 , oxo, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, or a heterocyclic group.

8. The process according claim 1 , wherein the cyclobutene has the structure IIIb or IIIb′, in which the cyclobutene of structure IIIb is isomerized to a cyclobutene of structure IIIb′

in the presence of an olefin metathesis catalyst;

wherein R b is selected from the group consisting of H, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 3 -C 8 cycloalkyl, heterocyclyl, aryl, aralkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 3 -C 6 cycloalkyloxy, aryloxy, heterocyclyloxy, C 1 -C 20 alkylamino, C 2 -C 20 alkenylamino, C 3 -C 8 cycloalkylamino, heterocyclylamino, or arylamino and may be substituted with up to three substituents selected from halo, CN, NO 2 , oxo, amino, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, or a heterocyclic group.

9. The process according to claim 1 , wherein the cyclobutene has the structure IIIc or IIIc′, in which the cyclobutene of structure IIIc is isomerized to a cyclobutene of structure IIIc′

in the presence of an olefin metathesis catalyst;

wherein R b is selected from the group consisting of H, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 3 -C 8 cycloalkyl, heterocyclyl, aryl, aralkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 3 -C 6 cycloalkyloxy, aryloxy, heterocyclyloxy, C 1 -C 20 alkylamino, C 2 -C 20 alkenylamino, C 3 -C 8 cycloalkylamino, heterocyclylamino, or arylamino and may be substituted with up to three substituents selected from halo, CN, NO 2 , oxo, amino, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, or a heterocyclic group;

m is an integer from 0 to 4, and

each R 8 is independently selected from the group consisting of aldehyde, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 3 -C 6 cycloalkyl, aryl, heterocyclyl, C 1 -C 20 alkoxy, C 1 -C 20 acyloxy, C 2 -C 20 alkenyloxy, C 3 -C 6 cycloalkyloxy, aryloxy, heterocyclyloxy, C 1 -C 20 alkylamino, C 2 -C 20 alkenylamino, C 3 -C 8 cycloalkylamino, heterocyclylamino, arylamino, or halogen; and adjacent substitutions of R 8 may be taken together to form a 5- to 7-membered ring which may be substituted with up to three substituents selected from halo, CN, NO 2 , oxo, amino, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, or a heterocyclic group.

10. The process according to claim 9 wherein the cyclohexene is selected from formula IIa and the cyclobutene of structure IIIc is selected from IIIc 1, IIIc2, III3,IIIc4, IIIc5, and IIIc6:

11. The process according to claim 7 , wherein R 5 and R 6 are taken together to form a cyclohexyl ring, which may be optionally substituted.

12. The process according to claim 2 , wherein R 5 and R 6 are taken together to form a cyclohexyl ring, which may be substituted.

13. The process according to claim 8 , wherein R 5 and R 6 are taken together to form a cyclohexyl ring, which may be substituted.