| 主权项 |
1. A method for the generation of oligomers or a mixture of oligomers to form a chemical library by amide-forming oligomerization comprising the steps of:
1) reacting a mixture of at least one initiator with at least one monomer to form a dimer of the initiator and the monomer or
to form a pre-oligomer with an initiator attached to a chain of more than one monomer, or a mixture thereof by amide-bond formation; 2) adding at least one terminator for the formation of a linear oligomer or a mixture of linear oligomers by amide-bond formation;
or, for the formation of a cyclic oligomer or a mixture of cyclic oligomers by amide-bond formation, changing the reaction conditions relative to step 1) so as to form a linking covalent bond between the at least one initiator and a monomer of the dimer or pre-oligomer formed in step 1), with the proviso that
step 2) can be omitted so that the dimer of the initiator and the monomer or the pre-oligomer with an initiator attached to a chain of more than one monomer, or a mixture thereof is formed as the linear oligomer or mixture of linear oligomers by amide-bond formation; wherein the initiator is selected from the group consisting of: with, for the formation of a linear oligomer or a mixture of linear oligomers by amide-bond formation, R being selected from the group consisting of: substituted or unsubstituted alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkylaryl, heteroalkylaryl, alkenyl, heteroalkenyl, alkinyl, heteroalkinyl, —C(NH2)RI, —C(NH2){RI—CO—C(NH2)}nRI with n=1, 2 and RI being H or an amino-acid side chain, fluorescent dye, nucleic acid or derivative thereof, peptide nucleic acid, FLAG octapeptide (DYKDDDDK), biotin or affinity tag; or with, for the formation of a cyclic oligomer or a mixture of cyclic oligomers by amide-bond formation, R being selected from the group consisting of: —{(CH2)}nRc, —{(CHCH3)}nRc, {(CH(1,1-dimethylethyl))}nRc, —{(CH(benzyl))}nRc, in each case with n=1,2 and Rc being a linker structure allowing to form a linking covalent amide bond to the respective terminal monomer of the dimer or oligomer formed in step 1); and in both cases with X+ being a counterion, selected from the group consisting of: K+, Cs+, Li+, Na+, R4N+, R4P+ or R3S+ with R being an organic substituent or H; X, Y, Z, being, independently from each other, selected from the group consisting of: F, OR, N+R3, N+R2OR, N+R2SR, and N+R2NR2, and including the situation of forming a cyclic or a bicyclic structure; wherein R is an organic substituent or H; or covalent dimers or trimers thereof with R in this case being a common linker element; wherein the monomer is selected from the group consisting of: with X being selected from the group consisting of: halogen, —OH, —COOH, —NH2, —O-Alkyl, —O-Aryl, —O—CO-Alkyl, —O—CO-Aryl, —SH, S-Alkyl, —S-Aryl, N-Acyl, —NH-Alkyl, —NH-Aryl, —N(Alkyl)2, —N(Aryl)2, —N(Alkyl)(Aryl), —CO—NH-Alkyl, —CO—NH-Aryl, —CO—N(Alkyl)2, —CO—N(Aryl)2, —CO—N(Alkyl)(Aryl), —CN, —NO2, —N3, —S(O)Aryl, —S(O)2 Aryl; Y being selected from the group consisting of: —PO3H, —COOH, —BF3−X+, —BXYZ, wherein X+, X, Y, Z are defined as given above in the context of the initiator, Z being selected from the group consisting of: —PO3H, —COOH, —BF3−X+, —BXYZ, wherein X+, X, Y, Z are defined as given above in the context of the initiator, as well as derivatives thereof which upon collapse of X and Z upon cleavage of the NO bond lead to Y; R being selected from the group consisting of: O, S, NR1, Si, CHR1R2; R1-R6 being, independently from each other, selected from the group consisting of: hydrogen, halogen, substituted or unsubstituted alkyl, heteroalkyl, aryl, cycloalkyl, heterocycloalkyl, heteroaryl, alkylaryl, heteroalkylaryl, alkenyl, heteroalkenyl, alkinyl, heteroalkinyl, as well as cyclic forms linking these among each other; Q being selected from the group consisting of: O, S, Si, NR1, where R1 is an organic substituent or H; and wherein the terminator, if used, is selected from the group consisting of: with R being selected from the group consisting of: CH2, (CH2)2, CHRT, CH2CHRT, (CH2)3, (CH2)2CHRT, CH2CHRTCH2, (CH2)4, wherein RT is selected from the group consisting of: hydrogen, halogen, substituted or unsubstituted alkyl, heteroalkyl, aryl, cycloalkyl, heterocycloalkyl, heteroaryl, alkylaryl, heteroalkylaryl, alkenyl, heteroalkenyl, alkinyl, heteroalkinyl; R1 being selected from the group consisting of: substituted or unsubstituted alkyl, heteroalkyl, aryl, cycloalkyl, heterocycloalkyl, heteroaryl, alkylaryl, heteroalkylaryl, alkenyl, heteroalkenyl, alkinyl, heteroalkinyl, ester, carbamate, sulfonate, sulfinate, phosphate, silyl; R7-R9 being, independently from each other, selected from the group consisting of: hydrogen, halogen, substituted or unsubstituted alkyl, heteroalkyl, aryl, cycloalkyl, heterocycloalkyl, heteroaryl, alkylaryl, heteroalkylaryl, alkenyl, heteroalkenyl, alkinyl, heteroalkinyl, ester, carbamate, sulfonate, sulfinate, phosphate, silyl, as well as cyclic forms linking these among each other and carbonyl, imidate, thiomidate or covalent dimers or trimers thereof with R1 and/or at least one of R7 or R8 in this case being a common linker element. |
