Functionalized isonitriles and products, preparation and uses thereof

A compound of formula (Ia),

• or a salt or solvate thereof,
• wherein each occurrence of,
• F is independently selected from a moiety comprising a photoactive or a biologically active moiety;
• and
• G is independently selected from a moiety of formula (II) or (III),
• wherein each occurrence of,
• R1, R1′, R2, R2′, R3, R3′ or R4 is independently selected from H, —COOR9, —C(═O)H, —CSR9, —C1-12 alkyl, —C1-6 alkyl-O—C1-6 alkyl, F, —C1-12 alkyl-F, —C1-6 alkyl-O—C1-6 alkyl-F, —C3-10 cycloalkyl, —C1-4 alkyl-C3-10 cycloalkyl, —C6-12 aryl, —C1-4 alkyl-C6-10 aryl, (5- to 10-membered)-C1-9 heteroaryl, —C1-4 alkyl-(5- to 10-membered)-C1-9 heteroaryl, (5- to 10-membered)-C2-9 heterocyclyl, or —C1-4 alkyl-(5- to 10-membered)-C2-9 heterocyclyl, wherein said alkyl, cycloalkyl, alkylcycloalkyl, aryl, alkylaryl, heteroaryl, alkylheteroaryl, heterocyclyl and alkylheterocyclyl groups are optionally substituted with 1, 2 or 3 substituents each independently selected from the group consisting of halogen, (═O), —OR9, —COOR9, —OC(═O)R9, —C(═O)H, —CN, —SR9, —N(R9)2, —N(R9)C(═O)H, —C(═O)N(R9)2, —ON(R9)2, and (5- to 10-membered)-C2-9 heterocyclyl with at least one N atom;
• n and x are integers independently selected from 0 to 6;
• Y and Y′ are independently selected from single bond, —CH(COOR9)—, —C(═O)—, —O—, —N(R5)— or optionally substituted phenyl;
• R5 is independently selected from H, —COOR9, —C(═O)H, —CSR9, —C1-12 alkyl, —C1-6 alkyl-O—C1-6 alkyl, —F, —C1-12 alkyl-F, —C1-6 alkyl-O—C1-6 alkyl-F, —C3-10 cycloalkyl, —C1-4 alkyl-C3-10 cycloalkyl, —C6-12 aryl, —C1-4 alkyl-C6-10 aryl, (5- to 10-membered)-C1-9 heteroaryl, —C1-4 alkyl-(5- to 10-membered)-C1-9 heteroaryl, (5- to 10-membered)-C2-9 heterocyclyl, or —C1-4 alkyl-(5- to 10-membered)-C2-9 heterocyclyl, wherein said alkyl, cycloalkyl, alkylcycloalkyl, aryl, alkylaryl, heteroaryl, alkylheteroaryl, heterocyclyl and alkylheterocyclyl groups are optionally substituted with 1, 2 or 3 substituents each independently selected from the group consisting of halogen, (═O), —OR9, —COOR9, —OC(═O)R9, —C(═O)H, —CN, —SR9, —N(R9)2, —N(R9)C(═O)H, —C(═O)N(R9)2, —ON(R9)2, and (5- to 10-membered)-C2-9 heterocyclyl with at least one N atom;
• W is independently selected from single bond, —N(R6)—, —N(R6)C(═O)—, —N(R6)—CH2O—, —ON(R6)—, —C(═O)N(R6)—, —C(═O)O(R7)—, —OC(═O)(R7)—, —C(═O)CH2O—, —CH2OC(═O)—, —C(═O)—, —O—, —C6-12 aryl-, or -(5- to 10-membered)-C2-9 heterocyclyl with at least one N atom-, wherein said aryl and heterocyclyl groups are optionally substituted with 1, 2 or 3 substituents each independently selected from the group consisting of halogen, (═O), —OR9, —COOR9, —OC(═O)R9, —C(═O)H, —CN, —SR9, —N(R9)2, —N(R9)C(═O)H, —C(═O)N(R9)2, —ON(R9)2, and (5- to 10-membered)-C2-9 heterocyclyl with at least one N atom;
• W′ is independently selected from single bond, —N(R6)—, —N(R6)C(═O)—, —N(R6)—CH2O—, —ON(R6)—, —C(═O)N(R6)—, —C(═O)O(R6)—, —OC(═O)(R6)—, —C(═O)—, —C(═O)O—, —O—, —C6-12 aryl- or -(5- to 10-membered)-C2-9 heterocyclyl with at least one N atom-, wherein said aryl and heterocyclyl groups are optionally substituted with 1, 2 or 3 substituents each independently selected from the group consisting of halogen, (═O), —OR9, —COOR9, —OC(═O)R9, —C(═O)H, —CN, —SR9, —N(R9)2, —N(R9)C(═O)H, —C(═O)N(R9)2, —ON(R9)2, and (5- to 10-membered)-C2-9 heterocyclyl with at least one N atom;
• R6 is independently selected from H, —C1-6 alkyl or —C6-12 aryl, wherein said alkyl and aryl groups are optionally substituted with 1, 2 or 3 substituents each independently selected from the group consisting of halogen, (═O), —OR9, —COOR9, —OC(═O)R9, —C(═O)H, —CN, —SR9, —N(R9)2, —N(R9)C(═O)H, —C(═O)N(R9)2, —ON(R9)2, and -(5- to 10-membered)-C2-9 heterocyclyl with at least one N atom;
• R7 is independently selected from —C2-C12 alkyl, optionally substituted with 1, 2 or 3 substituents each independently selected from the group consisting of halogen, (═O), —OR9, —COOR9, —OC(═O)R9, —C(═O)H, —CN, —SR9, —N(R9)2, —N(R9)C(═O)H, —C(═O)N(R9)2, —ON(R9)2, and -(5- to 10-membered)-C2-9 heterocyclyl with at least one N atom;
• E is independently selected from —R6 or —F;
• R9 is independently selected from H or C1-C4 alkyl;
• and
• wherein,
• R1 and R2, or R1′ and R2′, together with the nitrogen and carbon atoms to which they are attached, can form an optionally substituted 5- to 10-membered heterocyclic ring, wherein said heterocyclic ring optionally contains 1, 2, or 3 additional heteroatoms selected from the group consisting of N, S, or O;
• R1, or R1′, and R5, together with the nitrogen atoms to which they are attached, can form an optionally substituted 5- to 10-membered heterocyclic ring, wherein said heterocyclic ring optionally contains 1, 2, or 3 additional heteroatoms selected from the group consisting of N, S, or O, as long as W or W′ is not a bond;
• and
• R1, or R1′, and R6, together with the nitrogen atoms to which they are attached, can form an optionally substituted 5- to 10-membered heterocyclic ring, wherein said heterocyclic ring optionally contains 1, 2, or 3 additional heteroatoms selected from the group consisting of N, S, or O;
• L, when present, is selected from G-F or —NC,
• and wherein S′ is a moiety of formula (IV),
• wherein,
• b is an integer comprised between 1 and 3;
• c is an integer comprised between 0 and 20;
• d is an integer comprised between 0 and 1;
• e is an integer comprised between 0 and 20;
• f is an integer comprised between 0 and 3;
• Z is selected from C, N, —C3-C10 cycloalkyl, (5- to 10-membered)-C2-9 heterocyclyl, —C6-C12 aryl, or (5- to 10-membered)-C1-9 heteroaryl;
• and
• R8═H, C1-C5 optionally substituted alkyl, or a moiety of formula (V)
• wherein,
• g is selected from an integer comprised between 0 and 20;
• and
• h and h′ are each independently selected from an integer comprised between 0 and 3,
• and wherein,
• c+e is at least 1, or d=1, and
• at least one occurrence of F is different from any other occurrences of F.