Sulfurization reagents on solid supports

A method of preparing a solid-supported sulfurization reagent comprising the steps of:

• a. providing a solid-supported sulfonamide, wherein the solid-supported sulfonamide comprises the following moiety:
• wherein (P) is the backbone of a polymeric solid support;
• wherein X comprises a linker;
• wherein R1 comprises an alkyl group, a cycloalkyl group, an aryl group, or a heterocycle;
• b. providing a sulfenyl chloride having the formula Cl—S—R2,
• wherein R2 comprises an alkyl group, an aryl group, a methyleneacyloxy group having the formula —CH2—O—C(O)—R7, a methylene carbonate group having the formula —CH2—O—C(O)—OR8, or a methylene carbamate group having the formula —CH2—O—C(O)—NR9R10;
• wherein R7 comprises a saturated hydrocarbon residue having from 1 to 20 carbon atoms, an aromatic hydrocarbon residue having from 3 to 14 annular carbon atoms, or a heteroaromatic hydrocarbon residue having from 3 to 14 annular atoms, at least one of which is a nitrogen, oxygen, or sulfur atom;
• wherein R8 comprises a C1 to C20 alkyl group, cycloalkyl group, aryl group, or heteroaryl group;
• wherein R9 and R10 independently comprises hydrogen, an alkyl group, a cycloalkyl group, and aryl group, or a heteroaryl group;
• and
• c. reacting the solid-supported sulfonamide with the sulfenyl chloride to yield the solid-supported sulfurization reagent comprising the following moiety:

A method of preparing a second oligonucleotide, wherein the second oligonucleotide comprises at least one P—S bond, the method comprising:

• a. providing a first oligonucleotide containing at least one P—H bond;
• b. providing a solid-supported sulfurization reagent, wherein the solid-supported sulfurization reagent comprises the following moiety:
• wherein (P) is the backbone of a polymeric solid support;
• wherein X comprises a linker;
• wherein R1 comprises an alkyl group, a cycloalkyl group, an aryl group, or a heterocycle;
• wherein R2 comprises an alkyl group, an aryl group, a methyleneacyloxy group having the formula —CH2—O—C(O)—R7, a methylene carbonate group having the formula —CH2—O—C(O)—OR8, or a methylene carbamate group having the formula —CH2—O—C(O)—NR9R10;
• wherein R7 comprises a saturated hydrocarbon residue having from 1 to 20 carbon atoms, an aromatic hydrocarbon residue having from 3 to 14 annular carbon atoms, or a heteroaromatic hydrocarbon residue having from 3 to 14 annular atoms, at least one of which is a nitrogen, oxygen, or sulfur atom;
• wherein R8 comprises a C1 to C20 alkyl group, cycloalkyl group, aryl group, or heteroaryl group;
• wherein R9 and R10 independently comprises hydrogen, an alkyl group, a cycloalkyl group, and aryl group, or a heteroaryl group;
• and
• c. reacting the first oligonucleotide with the solid-supported sulfurization reagent, wherein the N—SR2 bond of the solid-supported sulfurization reagent is metathesized with the at least one P—H bond of the first oligonucleotide to yield the second oligonucleotide comprising at least one P—S bond and a solid-supported sulfonamide comprising an N—H bond.