Diels-alder adducts of epoxybutene and epoxybutene derivatives

A method of making a bicyclic compound selected from the group consisting of compounds of Formula XII and Formula XIII:

• 47
• wherein:
• R, R1, R2, R3, R4 and R5 are each independently selected from the group consisting of H, and C1-C4 lower alkyl;
• and
• R11 and R12 each independently represent —H, —OH, —OCOCH3, —OCH2C6H5, or —OR13 wherein R13 represents C1-C4 lower alkyl, or
• R11 and R12 together represent —O—, —O—C(O)—O— or —O—C(CH3)2—O—;
• comprising reacting a diene according to Formula II:
• 48
• wherein R, R1, R2, R3, R4 and R5 are as given above, with a dieneophile according to Formula VI:
• 49
• wherein R11 and R12 are as given above in a Diels-Alder reaction at a pressure greater than atmospheric pressure to yield a compound selected from the group consisting of compounds of Formula XII and compounds of Formula XIII.

A method of making a compound selected from the group consisting of compounds of Formula XIV and Formula XV:

• 50
• wherein:
• R6 is —H;
• R7 is —H or —CH3;
• and
• R11 and R12 each independently represent —H, —OH, —OAc —OCOCH3, —OCH2C6H5, or —OR13 wherein R13 represents C1-C4 lower alkyl, or
• R11 and R12 together represent —O—, —O—C(O)—O— or —O—C(CH3)2—O—. comprising reacting a diene of Formula III or Formula IV:
• 51
• with a dieneophile according to Formula VI:
• 52
• wherein R11 and R12 are as given above, in a Diels-Alder reaction at a pressure greater than atmospheric pressure to yield a compound selected from the group consisting of compounds of Formula XII and compounds of Formula XIII.

A method of making a bicyclic compound selected from the group consisting of compounds of Formula XVI and compounds of Formula XVII:

• 53
• wherein R, R1, R2, R3, R4, R13, R14, R15 and R16 are each independently selected from the group consisting of H, and C1-C4 lower alkyl;
• comprising
• reacting a diene according to Formula I:
• 54
• wherein R, R1, R2, R3, and R4 are as given above, with a dieneophile according to Formula VII:
• 55
• wherein R13, R14, R15 and R16 are as given above in a Diels-Alder reaction at a pressure greater than atmospheric pressure to yield a compound selected from the group consisting of compounds of Formula XVI and compounds of Formula XVII.

A method of making a bicyclic compound selected from the group consisting of compounds of Formula XVIII and compounds of Formula XIX:

• 56
• wherein R, R1, R2, R3, R4, R5, R13, R14, R15 and R16 are each independently selected from the group consisting of H, and C1-C4 lower alkyl;
• comprising
• reacting a diene according to Formula II:
• 57
• wherein R, R1, R2, R3, R4 and R5 are as given above, with a dieneophile according to Formula VII:
• 58
• wherein R13, R14, R15 and R16 are as given above in a Diels-Alder reaction at a pressure greater than atmospheric pressure to yield a compound selected from the group consisting of compounds of Formula XVIII and compounds of Formula XIX.

A method of making a compound according to Formula XX

• 59
• wherein R6 is —H, R7 is —H or —CH3, and R13, R14, R15 and R16 are each independently selected from the group consisting of H and C1-C4 alkyl;
• comprising reacting a diene of Formula III or Formula IV:
• 60
• with a dieneophile according to Formula VI:
• 61
• wherein R13, R14, R15 and R16 are as given above, in a Diels-Alder reaction at a pressure greater than atmospheric pressure to yield a compound of Formula XX.

A bicyclic compound selected from the group consisting of compounds of Formula X and compounds of Formula XI:

• 62
• wherein:
• R, R1, R2, R3, and R4 are each independently selected from the group consisting of H, and C1-C4 lower alkyl;
• and
• R11 and R12 each independently represent —H, —OH, —OCOCH3, —OCH2C6H5, or —OR13 wherein R13 represents C1-C4 lower alkyl, or
• R11 and R12 together represent —O—, —O—C(O)—O— or —O—C(CH3)2—O—;
• subject to the proviso that, when R1, R2, R3, and R4 are each H, then R11 and R12 are not together —O—.

A bicyclic compound selected from the group consisting of compounds of Formula XII and Formula XIII:

• 63
• wherein:
• R, R1, R2, R3, R4 and R5 are each independently selected from the group consisting of H, and C1-C4 lower alkyl;
• and
• R11 and R12 each independently represent —H, —OH, —OCOCH3, —OCH2C6H5, or —OR13 wherein R13 represents C1-C4 lower alkyl, or
• R11 and R12 together represent —O—, —O—C(O)—O— or O—C(CH3)2—O—.

A compound selected from the group consisting of compounds of Formula XIV and Formula XV:

• 64
• wherein:
• R6 is —H;
• R7 is —H or —CH3;
• and
• R11 and R12 each independently represent —H, —OH, —OAc —OCOCH3, —OCH2C6H5, or —OR13 wherein R13 represents C1-C4 lower alkyl, or
• R11 and R12 together represent —O—, —O—C(O)—O— or —O—C(CH3)2—O—.