α-carboxy caged compounds

Claim 2

A photolabile compound, having the formula ##STR4## wherein R 1 and R 2 , which may be the same or different, are H, --(C═O)--Cl, CO 2 R 7 ,--OR 8 , --O--(CH 2 ) n --CO 2 R 7 ; wherein R 7 is H, a linear or branched alkyl ester having 1-6 carbons, --CH 2 --O--(C═O)--CH 3 , or a carboxylate salt, and R 8 is a linear or branched alkyl having 1-18 carbons; n=1-17; R 3 is H or --NO 2 ; R 4 , is H, a linear or branched alkyl ester having 1-6 carbons, --CH 2 --O--(C═O)--CH 3 , or a carboxylate salt; X is ##STR5## and R 5 is selected so that photolysis of said photolabile compound generates a linear or branched, saturated or unsaturated, substituted or unsubstituted carboxylic acid that is a fatty acid having 3-32 carbons; or R 5 is selected so that photolysis of said photolabile compound generates a glutamic acid, an aspartic acid, or a γ-aminobutyric acid.

Claim 3

A compound, as claimed in claim 1 wherein said carboxylic acid is a prostaglandin.

Claim 4

A compound, as claimed in claim 1, wherein said carboxylic acid is arachidonic acid.

Claim 5

A compound, as claimed in claim 1, wherein said carboxylic acid is domoic acid.

Claim 6

A photolabile compound, having the formula ##STR6## wherein R 1 and R 2 which may be the same or different, are H, --(C═O)--Cl, CO 2 R 7 ,--OR 8 , --O--(CH 2 ) n --CO 2 R 7 , or R 1 and R 2 taken in combination are --O--CH 2 --O--; wherein R 7 is H, a linear or branched alkyl ester having 1-6 carbons, --CH 2 --O--(C═O)--CH 3 , ##STR7## or a carboxylate salt, and R 8 is a linear or branched alkyl having 1-18 carbons; n=1-17; R 3 is H or --NO 2 ; R 4 is H, a linear or branched alkyl ester having 1-6 carbons, --CH 2 --O--(C═O)--CH 3 , ##STR8## or a carboxylate salt; X is ##STR9## wherein R 5 and R 6 are selected so that photolysis of said photolabile compound generates an amino acid, peptide or protein; or X is ##STR10## and R 5 is selected so that photolysis of said photolabile compound generates a linear or branched, saturated or unsaturated, substituted or unsubstituted carboxylic acid that is a fatty acid having less than 32 carbons.

Claim 7

A photolabile compound, having the formula ##STR6## wherein R 1 and R 2 which may be the same or different, are H, --(C═O)--Cl, CO 2 R 7 ,--OR 8 , --O--(CH 2 ) n --CO 2 R 7 , or R 1 and R 2 taken in combination are --O--CH 2 --O--; wherein R 7 is H, a linear or branched alkyl ester having 1-6 carbons, --CH 2 --O--(C═O)--CH 3 , ##STR7## or a carboxylate salt, and R 8 is a linear or branched alkyl having 1-18 carbons; n=1-17; R 3 is H or --NO 2 ; R 4 is H, a linear or branched alkyl ester having 1-6 carbons, --CH 2 --O--(C═O)--CH 3 , ##STR8## or a carboxylate salt; X is ##STR9## wherein R 5 and R 6 are selected so that photolysis of said photolabile compound generates an amino acid, peptide or protein; or X is ##STR10## and R 5 is selected so that photolysis of said photolabile compound generates a linear or branched, saturated or unsaturated, substituted or unsubstituted carboxylic acid that is a fatty acid having less than 32 carbons.

Claim 8

A compound, as claimed in claim 5, wherein said amino acid is caged through a carboxylic acid as an ester.

Claim 9

A compound, as claimed in claim 5, wherein said amino acid is caged through a α-nitrogen or a non-α-nitrogen atom as a carbamate.

Claim 10

A compound, as claimed in claim 5, wherein said amino acid is caged through a side-chain hydroxyl as an ether or carbonate.

Claim 11

A compound, as claimed in claim 5, wherein said amino acid is caged through a side chain thiol as a thioether.

Claim 12

A compound, as claimed in claim 5, wherein R 1 and R 2 , which may be the same or different, are H, --(C═O)--Cl, --CO 2 R 7 ,--OR 8 , or --O--(CH 2 ) n --CO 2 R 7 ; wherein R 7 is H, a linear or branched alkyl ester having 1-6 carbons, --CH 2 --O--(C═O)--CH 3 , ##STR11## or a carboxylate salt, and R 8 is a linear or branched alkyl having 1-18 carbons; n=1-17; R 3 is H or --NO 2 ; R 4 is H, a linear or branched alkyl ester having 1-6 carbons, --CH 2 --O--(C═O)--CH 3 , ##STR12## or a carboxylate salt; X is --O--(C═O)--R 5 ; wherein R 5 is selected so that photolysis of said photolabile compound generates a serine, threonine, tyrosine, lysine, glutamic acid, or aspartic acid.

Claim 13

A compound, as claimed in claim 1, wherein R 1 , R 2 , R 3 and R 4 are hydrogen.

Claim 14

A photolabile compound, having the formula ##STR13## wherein R 1 and R 2 , which may be the same or different, are H, --(C═O)--Cl, --CO 2 R 7 --OR 8 , or --O--(CH 2 ) n --CO 2 R 7 , or R 1 and R 2 taken in combination are --O--CH 2 --O--; wherein R 7 is H, a linear or branched alkyl ester having 1-6 carbons, --CH 2 --O--(C═O)--CH 3 , ##STR14## or a carboxylate salt, and R 8 is a linear or branched alkyl having 1-18 carbons; n=1-17; R 3 is H or --NO 2 ; R 4 is H, a linear or branched alkyl ester having 1-6 carbons, --CH 2 --O--(C═O)--CH 3 , ##STR15## or a carboxylate salt; X is ##STR16## wherein R 5 and R 6 are selected so that photolysis of said photolabile compound generates a carbohydrate that is a monosaccharide, disaccharide or a polysaccharide.

Claim 15

A photolabile compound, having the formula ##STR13## wherein R 1 and R 2 , which may be the same or different, are H, --(C═O)--Cl, --CO 2 R 7 --OR 8 , or --O--(CH 2 ) n --CO 2 R 7 , or R 1 and R 2 taken in combination are --O--CH 2 --O--; wherein R 7 is H, a linear or branched alkyl ester having 1-6 carbons, --CH 2 --O--(C═O)--CH 3 , ##STR14## or a carboxylate salt, and R 8 is a linear or branched alkyl having 1-18 carbons; n=1-17; R 3 is H or --NO 2 ; R 4 is H, a linear or branched alkyl ester having 1-6 carbons, --CH 2 --O--(C═O)--CH 3 , ##STR15## or a carboxylate salt; X is ##STR16## wherein R 5 and R 6 are selected so that photolysis of said photolabile compound generates a carbohydrate that is a monosaccharide, disaccharide or a polysaccharide.

Claim 16

A compound, as claimed in claim 12, wherein said carbohydrate is caged as an ether or carbonate of an aliphatic hydroxyl group.

Claim 17

A compound, as claimed in claim 12, wherein said carbohydrate is caged as a carbamate of an amino group.

Claim 18

A compound, as claimed in claim 12, wherein said carbohydrate is caged as an ester of a carboxylic acid or of a phosphate or thiophosphate group.

Claim 19

A photolabile compound, having the formula ##STR17## wherein R 1 and R 2 , which may be the same or different, are H, --(C═O)-Cl, --CO 2 R 7 , --OR 8 , or --O--(CH 2 ) n --CO 2 R 7 , or R 1 and R 2 taken in combination are --O--CH 2 --O--; wherein R 7 is H, a linear or branched alkyl ester having 1-6 carbons, --CH 2 --O--(C═O)--CH 3 , ##STR18## or a carboxylate salt, and R 8 is a linear or branched alkyl having 1-18 carbons; n=1-17; R 3 is H or --NO 2 ; R 4 is H, a linear or branched alkyl ester having 1-6 carbons, --CH 2 --O--(C═O)--CH 3 , ##STR19## or a carboxylate salt; X is ##STR20## wherein R 5 and R 6 are selected so that photolysis of said photolabile compound generates a nucleoside, a nucleotide or an oligonucleotide.

Claim 20

A photolabile compound, having the formula ##STR17## wherein R 1 and R 2 , which may be the same or different, are H, --(C═O)-Cl, --CO 2 R 7 , --OR 8 , or --O--(CH 2 ) n --CO 2 R 7 , or R 1 and R 2 taken in combination are --O--CH 2 --O--; wherein R 7 is H, a linear or branched alkyl ester having 1-6 carbons, --CH 2 --O--(C═O)--CH 3 , ##STR18## or a carboxylate salt, and R 8 is a linear or branched alkyl having 1-18 carbons; n=1-17; R 3 is H or --NO 2 ; R 4 is H, a linear or branched alkyl ester having 1-6 carbons, --CH 2 --O--(C═O)--CH 3 , ##STR19## or a carboxylate salt; X is ##STR20## wherein R 5 and R 6 are selected so that photolysis of said photolabile compound generates a nucleoside, a nucleotide or an oligonucleotide.

Claim 21

A compound, as claimed in claim 16, wherein said nucleoside, nucleotide or oligonucleotide is caged as an ether or carbonate ester of a carbohydrate portion of said nucleoside, nucleotide or oligonucleotide; or caged as an ether or carbonate ester of a hydroxyl function attached directly or indirectly to a base portion of said nucleoside, nucleotide or oligonucleotide.

Claim 22

A compound, as claimed in claim 16, wherein said nucleoside, nucleotide or oligonucleotide is caged as a carbamate derivative at a nitrogen atom of a base portion of said nucleoside, nucleotide or oligonucleotide.

Claim 23

A compound, as claimed in claim 16, wherein said nucleotide or oligonucleotide is caged as a phosphate monoester, phosphodiester or thiophosphate at a phosphate portion of said nucleotide or oligonucleotide.

Claim 24

A photolabile compound, having the formula ##STR21## wherein R 1 and R 2 , which may be the same or different, are H, --(C═O)--Cl, --CO 2 R 7 , --OR 8 , or --O--(CH 2 ) n --CO 2 R 7 ; wherein R 7 is H, a linear or branched alkyl ester having 1-6 carbons, --CH 2 --O--(C═O)--CH 3 , ##STR22## or a carboxylate salt, and R 8 is a linear or branched alkyl having 1-18 carbons; n=1-17; R 3 is H or --NO 2 ; R 4 is H, a linear or branched alkyl ester having 1-6 carbons, --CH 2 --O--(C═O)--CH 3 , ##STR23## or a carboxylate salt; X is --O--(C═O)--R 5 ; wherein R 5 is selected so that photolysis of said photolabile compound generates a glutamic acid, an arachidonic acid, a γ-aminobutyric acid, a N-methyl-D-aspartic acid, a kainate, a 1-aminocyclopentane-1,3-dicarboxylate, a quisqualate, or a glucuronic acid.

Claim 25

A photolabile compound, having the formula ##STR21## wherein R 1 and R 2 , which may be the same or different, are H, --(C═O)--Cl, --CO 2 R 7 , --OR 8 , or --O--(CH 2 ) n --CO 2 R 7 ; wherein R 7 is H, a linear or branched alkyl ester having 1-6 carbons, --CH 2 --O--(C═O)--CH 3 , ##STR22## or a carboxylate salt, and R 8 is a linear or branched alkyl having 1-18 carbons; n=1-17; R 3 is H or --NO 2 ; R 4 is H, a linear or branched alkyl ester having 1-6 carbons, --CH 2 --O--(C═O)--CH 3 , ##STR23## or a carboxylate salt; X is --O--(C═O)--R 5 ; wherein R 5 is selected so that photolysis of said photolabile compound generates a glutamic acid, an arachidonic acid, a γ-aminobutyric acid, a N-methyl-D-aspartic acid, a kainate, a 1-aminocyclopentane-1,3-dicarboxylate, a quisqualate, or a glucuronic acid.

Claim 26

A compound, as claimed in claim 20, wherein R 1 , R 2 and R 3 are hydrogen.

Claim 27

A compound, as claimed in claim 20 wherein photolysis of said photolabile compound generates a glutamic acid, a γ-aminobutyric acid, a N-methyl-D-aspartic acid, a kainate, a 1-aminocyclopentane-1,3-dicarboxylate, or a quisqualate.

Claim 28

A photolabile compound, having the formula ##STR24## wherein R 1 and R 2 which may be the same or different, are H, --(C═O)--Cl, --CO 1 R 7 ,--OR 8 , or --O--(CH 2 ) n --CO 2 R 7 , or R 1 and R 2 taken in combination are --O--CH 2 --O--; wherein R 7 is H, a linear or branched alkyl ester having 1-6 carbons, --CH 2 --O--(C═O)--CH 3 , ##STR25## or a carboxylate salt, and R 8 is a linear or branched alkyl having 1-18 carbons; n=1-17; R 3 is H or --NO 2 ; R 4 is H, a linear or branched alkyl ester having 1-6 carbons, --CH 2 --O--(C═O)--CH 3 , ##STR26## or a carboxylate salt; and X is ##STR27##

Claim 29

A photolabile compound, having the formula ##STR24## wherein R 1 and R 2 which may be the same or different, are H, --(C═O)--Cl, --CO 1 R 7 ,--OR 8 , or --O--(CH 2 ) n --CO 2 R 7 , or R 1 and R 2 taken in combination are --O--CH 2 --O--; wherein R 7 is H, a linear or branched alkyl ester having 1-6 carbons, --CH 2 --O--(C═O)--CH 3 , ##STR25## or a carboxylate salt, and R 8 is a linear or branched alkyl having 1-18 carbons; n=1-17; R 3 is H or --NO 2 ; R 4 is H, a linear or branched alkyl ester having 1-6 carbons, --CH 2 --O--(C═O)--CH 3 , ##STR26## or a carboxylate salt; and X is ##STR27##