Narrow emission dyes, compositions comprising same, and methods for making and using same

A method of preparing a synthetic intermediate of a compound of Formula (II):

• wherein:
• M is a metal or is —H, —H;
• R5, R10, and R15 are independently selected from H, alkoxy, and a linker group having the formula:
• -L1-(X1-L2)p-G;
• wherein p is 0 or 1;
• L1 is alkylidene;
• X1 is —C(═O)NH— or —NHC(═O)—;
• L2 is —(CH2CH2O)q-alkylene-, wherein q is an integer between 1 and 24, alkylene, or substituted alkylene, optionally wherein substituted alkylene is alkylene substituted by a one or more groups comprising a polyoxyethylene chain and/or an amide group;
• and G is a bioconjugatable group;
• and
• R2, R3, R12, and R13 are independently selected from H, cyano, halo, perhaloalkyl, sulfonate, sulfonamide, ester, carboxylic acid, formyl, acetyl, a linker group having the formula -L1-(X1-L2)p-G, and a solubilizing group, wherein the solubilizing group is selected from -aryl-(Rs)w and -alkynyl-aryl-(Rs)w, wherein w is an integer between 0 and 5 inclusive, and RS is a group having the formula:
• —X2-(L3)z-R17,
• wherein:
• z is 0 or 1;
• X2 is —CH2NHC(═O)—, —C(═O)NH-alkylene-NH—, or triazolyl;
• L3 is —C(═O)-alkylene-C(═O)—NH—, and R17 is selected from —(C2H4O)m—R18, —C(═O)C2H4—(OC2H4)mOR18, and —(C2H4O)n—C2H4—C(═O)NH—C(R19)3, wherein m is an integer of 12 or more;
• n is an integer between 1 and 5;
• R18 is loweralkyl, optionally methyl;
• and R19 is —CH2O—C2H4—C(═O)NH—(C2H4O)mR18;
• subject to the proviso that at least one of R2, R3, R12, and R13 is -aryl-(Rs)w or -alkynyl-aryl-(Rs)w;
• wherein said method comprises:
• (a) providing a compound having the formula (II′):
• wherein:
• M is a metal or is —H, —H;
• R5′, R10′, and R15′ are independently selected from H, alkoxy,
• and
• R2′, R3′, R12′, and R13′ are independently selected from H, cyano, halo, perhaloalkyl, sulfonate, sulfonamide, ester, carboxylic acid, formyl, acetyl,
• subject to the proviso that at least one of R2′, R3′, R12′, and R13′ is
• and
• (b) contacting the compound provided in step (a) with a solution comprising 4 molar (M) HCl in dioxane to provide a compound of the formula (II″):
• wherein:
• M is a metal or is —H, —H;
• R5″, R10″, and R15″ are independently selected from H, alkoxy,
• and
• R2″, R3″, R12″, and R13″ are independently selected from H, cyano, halo, perhaloalkyl, sulfonate, sulfonamide, ester, carboxylic acid, formyl, acetyl,
• subject to the proviso that at least one of R2″, R3″, R12″, and R13″ is

A method of preparing an asymmetric bacteriochlorin compound having the formula:

• wherein:
• M is a metal or is —H, —H;
• R5, R10, and R15 are independently selected from H and alkoxy;
• and
• R2, R3, R12, and R13 are independently selected from H, cyano, halo, perhaloalkyl, sulfonate, sulfonamide, ester, carboxylic acid, formyl, acetyl, a linker group, and a solubilizing group;
• wherein the linker group has a formula:
• -L1-(X1-L2)p-G,
• wherein p is 0 or 1;
• L1 is alkylidene;
• X1 is —C(═O)NH— or —NHC(═O)—;
• L2 is —(CH2CH2O)q-alkylene-, wherein q is an integer between 1 and 24, alkylene, or substituted alkylene, optionally wherein substituted alkylene is alkylene substituted by a one or more groups comprising a polyoxyethylene chain and/or an amide group;
• and G is a bioconjugatable group;
• and wherein the solubilizing group is selected from -aryl-(Rs)w and -alkynyl-aryl-(Rs)w, wherein w is an integer between 0 and 5 inclusive, and RS is a group having the formula:
• —X2-(L3)z-R17,
• wherein:
• z is 0 or 1;
• X2 is —CH2NHC(═O)—, —C(═O)NH— alkylene-NH—, or triazolyl;
• L3 is —C(═O)-alkylene-C(═O)—NH—, and R17 is selected from —(C2H4O)m—R18, —C(═O)C2H4—(OC2H4)mOR18, and —(C2H4O)n—C2H4—C(═O)NH—C(R19)3, wherein m is an integer of 12 or more;
• n is an integer between 1 and 5;
• R18 is loweralkyl, optionally methyl;
• and R19 is —CH2O—C2H4—C(═O)NH—(C2H4O)mR18;
• subject to the proviso that R2 and R12 are not the same or R3 and R13 are not the same, and wherein at least one of R2, R3, R12, and R13 is -aryl-(Rs)w or -alkynyl-aryl-(Rs)w;
• wherein said method comprises:
• (a) providing a compound having the formula:
• wherein:
• M is a metal or is —H, —H;
• R5′, R10′, and R15′ are independently selected from H and alkoxy;
• and
• R2′, R3′, R12′, and R13′ are independently selected from H, cyano, halo, perhaloalkyl, sulfonate, sulfonamide, ester, carboxylic acid, formyl, and acetyl, wherein R2′ and R12, are each halo, optionally bromo, or wherein R3′ and R13′ are each halo, optionally bromo;
• and
• (b) contacting the compound with a palladium catalyst, a base, and one of:
• (i) two different alkynes, optionally wherein said two different alkynes are both compounds having the formula:
• wherein y is an integer between 1 and 5, optionally 1 or 2;
• and each R20 is an N-protected alkylamine, a protected carboxylic acid, —C(═O)—NH-alkylene-protected amine, or —C(═O)—NH-substituted alkylene-protected amine, optionally wherein the substituted alkylene of —C(═O)—NH-substituted alkylene-protected amine comprises protected carboxylic acid substituted alkylene;
• (ii) two different alkenes, optionally wherein said two different alkenes are both compounds having the formula:
• wherein y is an integer between 1 and 5, optionally 1 or 2;
• and each R20 is an N-protected alkylamine, a protected carboxylic acid, —C(═O)—NH-alkylene-protected amine, or —C(═O)—NH-substituted alkylene-protected amine, optionally wherein the substituted alkylene of —C(═O)—NH-substituted alkylene-protected amine comprises protected carboxylic acid substituted alkylene;
• and
• (iii) two different organic boronates;
• optionally wherein said two different organic boronates are two different aryl boronic acids or aryl boronic esters of the formula:
• wherein y is an integer between 1 and 5, optionally 1 or 2;
• each R20 is an N-protected alkylamine, a protected carboxylic acid, —C(═O)—NH-alkylene-protected amine, or —C(═O)—NH-substituted alkylene-protected amine, optionally wherein the substituted alkylene of —C(═O)—NH-substituted alkylene-protected amine comprises protected carboxylic acid substituted alkylene;
• and each R21 is H or alkyl or wherein two R21 together form an alkylene.