Environmentally-friendly hydroazidation of olefins

A process for preparing an organic azide of Formula III comprising mixing an olefin of Formula I, a silylazide of Formula II, a hydrogen bond donor, and an organic promoter:

• wherein:
• R1 and R2 are independently selected from hydrogen, alkyl, cycloalkyl, heteroalkyl, and heterocycloalkyl, wherein each of R1 and R2 that is not hydrogen is optionally substituted with one or more substituents selected from oxo, halo, cyano, azido, nitro, R7, —OR7, —N(R7)(R7), —(C═O)R7, —(C═O)OR7, —(C═O)N(R7)(R7), —O(C═O)R7, —N(R7)(C═O)R7, —O(C═O)N(R7)(R7), and —N(R7)(C═O)OR7;
• wherein at least one of R1 and R2 is not hydrogen;
• R3 is selected from hydrogen, alkyl, cycloalkyl, heteroalkyl, and heterocycloalkyl, wherein R3 other than hydrogen is optionally substituted with one or more substituents selected from oxo, halo, cyano, azido, nitro, R7, —OR7, —N(R7)(R7), —(C═O)R7, —(C═O)OR7, —(C═O)N(R7)(R7), —O(C═O)R7, —N(R7)(C═O)R7, —O(C═O)N(R7)(R7), and —N(R7)(C═O)OR7;
• or
• R1 and R2 or R2 and R3 are taken together with the carbons to which they are attached to form a cycloalkyl ring or an heterocycloalkyl ring, wherein each cycloalkyl or heterocycloalkyl ring is optionally substituted with one or more substituents selected from oxo, halo, cyano, azido, nitro, R7, —OR7, —N(R7)(R7), —(C═O)R7, —(C═O)OR7, —(C═O)N(R7)(R7), —O(C═O)R7, —N(R7)(C═O)R7, —O(C═O)N(R7)(R7), and —N(R7)(C═O)OR7;
• R4 is independently selected at each occurrence from alkyl and cycloalkyl;
• the organic promoter is selected from:
• R5 is independently selected from hydrogen, halo, cyano, azido, nitro, R7, —OR', —N(R7)(R7), —(C═O)R7, —(C═O)OR7, —(C═O)N(R7)(R7), —O(C═O)R7, —N(R7)(C═O)R7, —O(C═O)N(R7)(R7), and —N(R7)(C═O)OR7;
• m is 1, 2, 3, or 4;
• Z is I;
• R6 and R6′ are independently selected from —O(C═O)R7, —O(SO2)(R7), hydroxyl, and azido;
• R7 is independently selected at each occurrence from hydrogen, alkyl, aryl, heteroalkyl, heteroaryl, cycloalkyl, heterocycloalkyl, and trialkylsilyl, each of which R7 other than hydrogen is optionally substituted with one or more substituents selected from alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, amino, alkylamino, dialkylamino, hydroxyl, halo, acylamino, aminoacyl, cyano, nitro, azido, acyl, acyloxy, carboxyl, carboxyl ester, alkanoyl, carboxamide, haloalkyl, and haloalkoxy;
• or
• two R7 groups may be brought together with the atoms to which they are attached to form a cycloalkyl, heterocycloalkyl, aryl, or heteroaryl ring, each of which ring is optionally substituted with one or more substituents selected from alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, amino, alkylamino, dialkylamino, hydroxyl, halo, acylamino, aminoacyl, cyano, nitro, azido, acyl, acyloxy, carboxyl, carboxyl ester, alkanoyl, carboxamide, haloalkyl, and haloalkoxy;
• R8 and R8′ are independently selected from hydrogen, halo, cyano, azido, nitro, R7, —OR7, —N(R7)(R7), —(C═O)R7, —(C═O)OR7, —(C═O)N(R7)(R7), —O(C═O)R7, —N(R7)(C═O)R7, —O(C═O)N(R7)(R7), and —N(R7)(C═O)OR7;
• or
• R8 and R8′ may be brought together with the carbon to which they are attached to form a cycloalkyl or heterocycloalkyl ring, each of which ring is optionally substituted with one or more substituents selected from oxo, halo, cyano, azido, nitro, R7, —OR', —N(R7)(R7), —(C═O)R7, —(C═O)OR7, —(C═O)N(R7)(R7), —O(C═O)R7, —N(R7)(C═O)R7, —O(C═O)N(R7)(R7), and —N(R7)(C═O)OR7;
• or
• R8 and R8′ are brought together to form an oxo or imino group;
• R9 is aryl or heteroaryl, wherein R9 is optionally substituted with one or more substituents selected from oxo, halo, cyano, azido, nitro, R7, —OR', —N(R7)(R7), —(C═O)R7, —(C═O)OR7, —(C═O)N(R7)(R7), —O(C═O)R7, —N(R7)(C═O)R7, —O(C═O)N(R7)(R7), and —N(R7)(C═O)OR7;
• and
• the hydrogen bond donor is water and optionally a second hydrogen bond donor.