Spirocyclic ligands for sigma receptors, and libraries and methods of use thereof

A compound represented by structure 6:

• wherein
• R represents independently for each occurrence hydrogen;
• alkyl;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three are S, O and/or N;
• aralkyl;
• or monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three are S, O and/or N;
• R1 is absent, or present between 1 and 4 times;
• R1 represents independently for each occurrence a halide;
• alkyl;
• alkenyl;
• alkynyl;
• hydroxyl;
• alkoxyl;
• silyloxy;
• amino;
• nitro;
• sulfhydryl;
• —R9SR8;
• —C(R8)═NR8;
• —N═C(R8)2;
• —C(O)N(R8)2;
• —Q2—P(Q1)(OR8)2;
• —Q2—P(Q1)R8(OR8);
• —P(R8)3;
• carboxyl;
• —R9C(O)OC(O)R8;
• silyl;
• —SR8;
• alkylsulfonyl;
• arylsulfonyl;
• —SeR8;
• —R9C(O)R8;
• —R9C(O)H;
• —R9C(O)OR;
• —OC(O)R;
• heteroalkyl;
• —R9CN;
• —R9NHC(═NH)NH2;
• —R9C(═NH)NH2;
• —R9CH(OR8)2;
• —R9C(OR8)2;
• —O—N(R8)3;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three ring atoms are selected independently from the group consisting of S, O, and N;
• aralkyl;
• monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three ring atoms are selected independently from the group consisting of S, O, and N;
• —N3;
• —R9CH(NH)CH2;
• —N(8)C(O)OR8;
• —R9OC(O)N(R8)2;
• —R9CH(O)CH2;
• —R9C(O)N(R8)OH;
• —ON(R8)C(O)R8;
• —R9C(O)N(R8)C(O)R8;
• —N(C(O)R8)2;
• —R9C(R8)═NOH;
• —N(R8)S(O)2R8;
• —C(S)N(R8)2;
• —N(R8)C(S)R8;
• —N(R8)C(O)N(R8)2;
• —N(R8)C(S)N(R8)2;
• or —(CH2)m—R80;
• R2 and R3 represent independently for each occurrence hydrogen;
• alkyl;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three are S, O and/or N;
• aralkyl;
• monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three are S, O and/or N;
• OR;
• N(R)2;
• CO2R;
• C(O)N(R)2;
• OC(O)R;
• or N(R)C(O)R;
• or the geminal instances of R2 and R3 taken together represents O;
• R6 represents hydrogen;
• alkyl;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three are S, O and/or N;
• aralkyl;
• monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three are S, O and/or N;
• acyl;
• C(O)OR;
• C(O)N(R)2;
• or SO2R;
• R7 represents hydrogen;
• alkyl;
• alkenyl;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three are S, O and/or N;
• aralkyl;
• monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three are S, O and/or N;
• acyl;
• C(O)OR;
• C(O)N(R)2;
• or SO2R;
• R80 represents independently for each occurrence an aryl, cycloalkyl, cycloalkenyl, heterocyclyl, or polycyclyl group comprised of 10 to 20 ring atoms, of which 0 to 6 are S, O and/or N and the remainder carbon;
• R8 represents independently for each occurrence hydrogen, alkyl, alkenyl, alkynyl, or aryl;
• R9 represents independently for each occurrence a bond or an alkyl, alkenyl, alkynyl, or aryl biradical;
• Q1 represents independently for each occurrence S or O;
• Q2 represents independently for each occurrence O, S, or NR8;
• and
• m is independently for each occurrence an integer in the range 0 to 8 inclusive;
• provided that R2 and R3 are not both methyl;
• or R6 and R7 are not both acetyl.

A compound represented by structure 7:

• wherein
• R represents independently for each occurrence hydrogen;
• alkyl;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three are S, O and/or N;
• aralkyl;
• or monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three are S, O and/or N;
• R1 is absent, or present between 1 and 4 times;
• R1 represents independently for each occurrence a halide;
• alkyl;
• alkenyl;
• alkynyl;
• hydroxyl;
• alkoxyl;
• silyloxy;
• amino;
• nitro;
• sulfhydryl;
• —R9SR8;
• —C(R8)═NR9;
• —N═C(R8)2;
• —C(O)N(R8)2;
• —Q2—P(Q1)(OR8)2;
• —Q2—P(Q1)R8(OR8);
• —P(R8)3;
• carboxyl;
• —R9C(O)OC(O)R8;
• silyl;
• —SR8;
• alkylsulfonyl;
• arylsulfonyl;
• —SeR8;
• —R9C(O)R8;
• —R9C(O)H;
• —R9C(O)OR;
• —OC(O)R;
• heteroalkyl;
• —R9CN;
• —R9NHC(═NH)NH2;
• —R9C(═NH)NH2;
• —R9CH(OR8)2;
• —R9C(OR8)2R8;
• —O—N(R8)3;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three ring atoms are selected independently from the group consisting of S, O, and N;
• aralkyl;
• monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three ring atoms are selected independently from the group consisting of S, O, and N;
• —N3;
• —R9CH(NH)CH2;
• —N(R8)C(O)OR8;
• —R9OC(O)N(R8)2;
• —R9CH(O)CH2;
• —R9C(O)N(R8)OH;
• —ON(R8)C(O)R8;
• —R9C(O)N(R8)C(O)R8;
• —N(C(O)R8)2;
• —R9C(R8)═NOH;
• —N(R8)S(O)2R8;
• —C(S)N(R8)2;
• —N(R8)C(S)R8:
• —N(R8)C(S)R8)2;
• —N(R8)C(S)N(R8)2;
• or —(CH2)m—R80;
• R2 and R3 represent independently for each occurrence hydrogen;
• alkyl;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three are S, O and/or N;
• aralkyl;
• monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three are S, O and/or N;
• OR;
• N(R)2;
• CO2R;
• C(O)N(R)2;
• OC(O)R;
• or N(R)C(O)R;
• or the geminal instances of R2 and R3 taken together represents C(R)2;
• R6 represents alkyl;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three are S, O and/or N;
• aralkyl;
• monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three are S, O and/or N;
• acyl;
• C(O)OR;
• C(O)N(R)2;
• or SO2R;
• R7 represents hydrogen;
• alkyl;
• alkenyl;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three are S, O and/or N;
• aralkyl;
• monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three are S, O and/or N;
• acyl;
• C(O)OR;
• C(O)N(R)2;
• or SO2R;
• R80 represents independently for each occurrence an aryl, cycloalkyl, cycloalkenyl, heterocyclyl, or polycyclyl group comprised of 10 to 20 ring atoms, of which 0 to 6 are S, O and/or N and the remainder carbon;
• R8 represents independently for each occurrence hydrogen, alkyl, alkenyl, alkynyl, or aryl;
• R9 represents independently for each occurrence a bond or an alkyl, alkenyl, alkynyl, or aryl biradical;
• Q1 represents independently for each occurrence S or O;
• Q2 represents independently for each occurrence O, S, or NR8;
• and
• m is independently for each occurrence an integer in the range 0 to 8 inclusive;
• provided that R2 and R3 are not both methyl;
• or R6 and R7 are not both acetyl.

A compound represented by structure 8:

• wherein
• R represents independently for each occurrence hydrogen;
• alkyl;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three are S, O and/or N;
• aralkyl;
• or monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three are S, O and/or N;
• R1 is absent, or present between 1 and 4 times;
• R1 represents independently for each occurrence a halide;
• alkyl;
• alkenyl;
• alkynyl;
• hydroxyl;
• alkoxyl;
• silyloxy;
• amino;
• nitro;
• sulfhydryl;
• —R9SR8;
• —C(R8)═NR8;
• —N═C(R8)2;
• —C(O)N(R8)2;
• —Q2—P(Q1)(OR8)2;
• —Q2—P(Q1)R8(OR8);
• —P(R8)3;
• carboxyl;
• —R9C(O))C(O)R8;
• silyl;
• —SR8;
• alkylsulfonyl;
• arylsulfonyl;
• —SeR8;
• —R9C(O)R8;
• —R9C(O)H;
• —R9C(O)OR;
• —OC(O)R;
• heteroalkyl;
• —R9CN;
• —R9NHC(═NH)NH2;
• —R9C(═NH)NH2;
• —R9CH(OR8)2;
• —R9C(OR8)2R8;
• —O—N(R8)3;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three ring atoms are selected independently from the group consisting of S, O, and N;
• aralkyl;
• monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three ring atoms are selected independently from the group consisting of S, O, and N;
• —N3;
• —R9CH(NH)CH2;
• —N(R8)C(O)OR8;
• —R9OC(O)N(R8)2;
• —R9CH(O)CH2;
• —R9C(O)N(R8)OH;
• —ON(R8)C(O)R8;
• —R9C(O)N(R8)C(O)R8;
• —N(C(O)R8)2;
• —R9C(R8)═NOH;
• —N(R8)S(O)2R8;
• —C(S)N(R8)2;
• —N(R8)C(S)R8;
• —N(R8)C(O)N(R8)2;
• —N(R8)C(S)N(R8)2;
• or —(CH2)m—R80;
• R2 and R3 represent independently for each occurrence hydrogen;
• alkyl;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three are S, O and/or N;
• aralkyl;
• monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three are S, O and/or N;
• OR;
• N(R)2;
• CO2R;
• C(O)N(R)2;
• OC(O)R;
• or N(R)C(O)R;
• or the geminal instances of R2 and R3 taken together represents C(R)2;
• R6 represents hydrogen;
• alkyl;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three are S, O and/or N;
• aralkyl;
• monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three are S, O and/or N;
• acyl;
• C(O)OR;
• C(O)N(R)2;
• or SO2R;
• R7 represents hydrogen;
• alkyl;
• alkenyl;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three are S, O and/or N;
• monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three are S, O and/or N;
• acyl;
• C(O)N(R)2;
• or SO2R;
• R80 represents independently for each occurrence an aryl, cycloalkyl, cycloalkenyl, heterocyclyl, or polycyclyl group comprised of 10 to 20 ring atoms, of which 0 to 6 are S, O and/or N and the remainder carbon;
• R8 represents independently for each occurrence hydrogen, alkyl, alkenyl, alkynyl, or aryl;
• R9 represents independently for each occurrence a bond or an alkyl, alkenyl, alkynyl, or aryl biradical;
• Q1 represents independently for each occurrence S or O;
• Q2 represents independently for each occurrence O, S, or NR8;
• and
• m is independently for each occurrence an integer in the range 0 to 8 inclusive.

A compound represented by structure 9:

• wherein
• R represents independently for each occurrence hydrogen;
• alkyl;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three are S, O and/or N;
• aralkyl;
• or monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three are S, O and/or N;
• R1 is absent, or present between 1 and 4 times;
• R1 represents independently for each occurrence a halide;
• alkyl;
• alkenyl;
• alkynyl;
• hydroxyl;
• alkoxyl;
• silyloxy;
• amino;
• nitro;
• sulfhydryl;
• —R9SR8;
• —C(R8)═NR8;
• —N═C(R8)2;
• —C(O)N(R8)2;
• —Q2—P(Q1)(OR8)2;
• —Q2—P(Q1)R8(OR8);
• —P(R8)3;
• carboxyl;
• —R9C(O)OC(O)R8;Silgl;
• —SR8;
• alkylsulfonyl;
• arylsulfonyl;
• —SeR8;
• —R9C(O)R8;
• —R9C(O)H;
• —R9C(O)OR;
• —OC(O)R;
• heteroalkyl;
• —R9CN;
• —R9NHC(═NH)NH2;
• —R9C(═NH)NH2;
• —R9CH(OR8)2;
• —RC(OR8)2R8;
• —O—N(R8)3;
• aryl;
• monocyclie or bicyclic heteroaryl with 5-12 ring atoms, of which one to three ring atoms are selected independently from the group consisting of S, O, and N;
• aralkyl;
• monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three ring atoms are selected independently from the group consisting of S, O, and N;
• —N3;
• —R9CH(NH)CH2;
• —N(R8)C(O)OR8;
• —R9OC(O)N(R8)2;
• —R9CH(O)CH2;
• —R9C(O)N(R8)OH;
• —ON(R8)C(O)R8;
• —R9C(O)N(R8)C(O)R8;
• —N(C(O)R8)2;
• —R9C(R8)═NOH;
• —N(R8)S(O)2R8;
• —C(S)N(R8)2;
• —N(R8)C(S)R8;
• —N(R8)C(O)N(R8)C(O)R8)2—N(R8)C(S)N(R8)2;
• or —(CH2)m—R80;
• R2 and R3 represent independently for each occurrence hydrogen;
• alkyl;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three are S, O and/or N;
• aralkyl, monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three are S, O and/or N;
• OR;
• N(R)2;
• CO2R;
• C(O)N(R)2;
• OC(O)R;
• or N(R)C(O)R;
• or the geminal instances of R2 and R3 taken together represents C(R)2;
• R6 represents alkyl;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three are S, O and/or N;
• aralkyl;
• monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three are S, O and/or N;
• acyl;
• C(O)OR;
• C(O)N(R)2;
• or SO2R;
• R7 represents C(O)OR;
• R80 represents independently for each occurrence an aryl, cycloalkyl, cycloalkenyl, heterocyclyl, or polycyclyl group comprised of 10 to 20 ring atoms, of which 0 to 6 are S, O and/or N and the remainder carbon;
• R8 represents independently for each occurrence hydrogen, alkyl, alkenyl, alkynyl, or aryl;
• R9 represents independently for each occurrence a bond or an alkyl, alkenyl, alkynyl, or aryl biradical;
• Q1 represents independently for each occurrence S or O;
• Q2 represents independently for each occurrence O, S, or NR8;
• and
• m is independently for each occurrence an integer in the range 0 to 8 inclusive.

A compound represented by structure 10:

• wherein
• R represents independently for each occurrence hydrogen;
• alkyl;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three are S, O and/or N;
• aralkyl;
• or monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three are S, O and/or N;
• R1 is absent, or present between 1 and 4 times;
• R1 represents independently for each occurrence a halide;
• alkyl;
• alkenyl;
• alkynyl;
• hydroxyl;
• alkoxyl;
• silyloxy;
• amino;
• nitro;
• sulfhydryl;
• —R9SR8;
• —C(R8)═NR8;
• —N═C(R8)2;
• —C(O)N(R8)2;
• —Q2—P(Q1)(OR8)2;
• —Q2—P(Q1)R8(OR8);
• —P(R8)3;
• carboxyl;
• —R9C(O)OC(O)R8;
• silyl;
• —SR8;
• alkylsulfonyl;
• arylsulfonyl;
• —SeR8;
• —R9C(O)R8;
• —R9C(O)H;
• —R9C(O)OR;
• —OC(O)R;
• heteroalkyl;
• —R9CN;
• —R9NHC(═NH)NH2;
• —R9C(═NH)NH2;
• —R9CH(OR8)2;
• —R—C(OR8)2R8;
• —O——N(R8)3;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three ring atoms are selected independently from the group consisting of S, O, and N;
• aralkyl;
• monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three ring atoms are selected independently from the group consisting of S, O, and N;
• —N3;
• —R9CH(NH)CH2;
• —N(R8)C(O)OR8;
• —R9OC(O)N(R8)2;
• —R9CH(O)CH2;
• —R9C(O)N(R8)OH;
• —ON(R8)C(O)R8;
• —R9C(O)N(R8)C(O)R8;
• —N(C(O)R8)2;
• —R9C(R8)═NOH;
• —N(R8)S(O)2R8;
• —C(S)N(R8)2;
• —N(R8)C(S)R8;
• —N(R8)C(O)N(R8)2;
• —N(R8)C(S)N(R8)2;
• or —(CH2)m—R80;
• R2 and R3 represent independently for each occurrence hydrogen;
• alkyl;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three are S, O and/or N;
• aralkyl;
• monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three are S, O and/or N;
• OR;
• N(R)2;
• CO2R;
• C(O)N(R)2;
• OC(O)R;
• or N(R)C(O)R;
• or the geminal instances of R2 and R3 taken together represents O;
• R6 represents aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three are S, O and/or N;
• monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three are S, O and/or N;
• C(O)OR;
• C(O)N(R)2;
• or SO2R;
• R7 represents C(O)OR or aralkyl;
• R80 represents independently for each occurrence an aryl, cycloalkyl, cycloalkenyl, heterocyclyl, or polycyclyl group comprised of 10 to 20 ring atoms, of which 0 to 6 are S, O and/or N and the remainder carbon;
• R8 represents independently for each occurrence hydrogen, alkyl, alkenyl, alkynyl, or aryl;
• R9 represents independently for each occurrence a bond or an alkyl, alkenyl, alkynyl, or aryl biradical;
• Q1 represents independently for each occurrence S or O;
• Q2 represents independently for each occurrence O, S, or NR8;
• and
• m is independently for each occurrence an integer in the range 0 to 8 inclusive.

A compound represented by structure 2:

• wherein
• R represents independently for each occurrence hydrogen;
• alkyl;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three are S, O and/or N;
• aralkyl;
• or monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three are S, O and/or N;
• R1 is absent, or present between 1 and 4 times;
• R1 represents independently for each occurrence a halide;
• alkyl;
• alkenyl;
• alkynyl;
• hydroxyl;
• alkoxyl;
• silyloxy;
• amino;
• nitro;
• sulfhydryl;
• —R9SR8;
• —C(R8)═NR8;
• —N═C(R8)2;
• —C(O)N(R8)2;
• —Q2—P(Q1)(OR8)2;
• —Q2—P(Q1)R8(OR8);
• —P(R8)3;
• carboxyl;
• —R9C(O)OC(O)R8;
• silyl;
• —SR8;
• alkylsulfonyl;
• arylsulfonyl;
• —SeR8;
• —R9(O)CR8;
• —R9C(O)H;
• —R9C(O)OR;
• —OC(O)R;
• heteroalkyl;
• —R9CN;
• —R9NHC(═NH)NH2;
• —R9C(═NH)NH2;
• —R9CH(OR8)2;
• —R9C(OR8)2R8;
• —O—N(R8)3;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three ring atoms are selected independently from the group consisting of S, O, and N;
• aralkyl;
• monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three ring atoms are selected independently from the group consisting of S, O, and N;
• —N3;
• —R9CH(NH)CH2;
• —N(R8)C(O)OR8;
• —R9C(O)N(R8)2;
• —R9CH(O)CH2;
• —R9C(O)N(R8)OH;
• —ON(R8)C(O)R8;
• —R9C(O)N(R8)C(O)R8;
• —N(C(O)R8)2;
• —R9C(R8)═NOH;
• —N(R8)S(O)2R8;
• —C(S)N(R8)2;
• —N(R8)C(S)R8;
• —N(R8)C(O)N(R8)2;
• N(R8)C(S)N(R8)2;
• or —(CH2)m—R80;
• R2 and R3 represent independently for each occurrence hydrogen;
• alkyl;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three are S, O and/or N;
• aralkyl;
• monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three are S, O and/or N;
• OR;
• N(R)2;
• CO2R;
• C(O)N(R)2;
• OC(O)R;
• or N(R)C(O)R;
• or the geminal instances of R2 and R3 taken together may represent O or C(R)2;
• R6 represents hydrogen;
• alkyl;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three are S, O and/or N;
• aralkyl;
• monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three are S, O and/or N;
• acyl;
• C(O)OR;
• C(O)N(R)2;
• or SO2R;
• R7 represents hydrogen;
• alkyl;
• alkenyl;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three are S, O and/or N;
• aralkyl;
• monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three are S, O and/or N;
• acyl;
• C(O)OR;
• C(O)N(R)2;
• or SO2R;
• R80 represents independently for each occurrence an aryl, cycloalkyl, cycloalkenyl, heterocyclyl, or polycyclyl group comprised of 10 to 20 ring atoms, of which 0 to 6 are S, O and/or N and the remainder carbon;
• R8 represents independently for each occurrence hydrogen, alkyl, alkenyl, alkynyl, or aryl;
• R9 represents independently for each occurrence a bond or an alkyl, alkenyl, alkynyl, or aryl biradical;
• Q1 represents independently for each occurrence S or O;
• Q2 represents independently for each occurrence O, S, or NR8;
• and
• m is independently for each occurrence an integer in the range 0 to 8 inclusive;
• provided that when the geminal instances of R2 and R3 taken together represent O, R7 is not acetyl.

A compound represented by structure 3:

• wherein
• R represents independently for each occurrence hydrogen, alkyl, aryl, heteroaryl, aralkyl, or heteroaralkyl;
• R1 is absent, or present between 1 and 4 times;
• R1 represents independently for each occurrence a halide;
• alkyl;
• alkenyl;
• alkynyl;
• hydroxyl;
• alkoxyl;
• silyloxy;
• amino;
• nitro;
• sulfhydryl;
• —R9SR8;
• —C(R)═NR8;
• —N═C(R8)2;
• —C(O)N(R8)2;
• —Q2—P(Q1)(OR8)2;
• —Q2—P(Q1)R8(OR8);
• —P(R8)3;
• carboxyl;
• —RC(O)OC(O)R8;
• SR8;
• alkylsulfonyl;
• arylsulfonyl;
• —SeR8;
• —R9(O)CR8;
• —R9C(O)H;
• —R9C(O)OR;
• —OC(O)R;
• heteroalkyl;
• —R9CN;
• —R9NHC(═NH)NH2;
• —R9C(═NH)NH2;
• —R9CH(OR8)2;
• —R9C(OR8)2R8;
• —O—N(R8)3;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three ring atoms are selected independently from the group consisting of S, O, and N;
• aralkyl;
• monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three ring atoms are selected independently from the group consisting of S, O, and N;
• —N3;
• —R9CH(NH)CH2;
• —N(R8)C(O)OR8;
• —R9OC(O)N(R8)2;
• —R9CH(O)CH2;
• —R9C(O)N(R8)OH;
• —ON(R8)C(O)R8;
• —R C(O)N(R8)C(O)R8;
• —N(C(O)R8)2;
• —R9C(R8)═NOH;
• —N(R8)S(O)2R8;
• —C(S)N(R8)2;
• —N(R8)C(S)R8;
• —N(R8)C(O)N(R8)2;
• —N(R8)C(S)N(R8)2;
• or —(CH2)m——R80;
• R2 and R3 represent independently for each occurrence hydrogen, alkyl, aryl, heteroaryl, aralkyl, heteroaralkyl, OR, N(R)2, CO2R, C(O)N(R)2, OC(O)R, or N(R)C(O)R;
• or the geminal instances of R2 and R3 taken together may represent O or C(R)2;
• R4 represents independently for each occurrence H or alkyl;
• R6 represents hydrogen, alkyl, aryl, heteroaryl, aralkyl, heteroaralkyl, acyl, C(O)OR, C(O)N(R)2, or SO2R;
• R7 represents hydrogen, alkyl, alkenyl, aryl, heteroaryl, aralkyl, heteroaralkyl, acyl, C(O)OR, C(O)N(R)2, or SO2R;
• R80 represents independently for each occurrence an aryl, cycloalkyl, cycloalkenyl, heterocyclyl, or polycyclyl group comprised of 10 to 20 ring atoms, of which 0 to 6 are S, O and/or N and the remainder carbon;
• R8 represents independently for each occurrence hydrogen, alkyl, alkenyl, alkynyl, or aryl;
• R9 represents independently for each occurrence a bond or an alkyl, alkenyl, alkynyl, or aryl biradical;
• Q1 represents independently for each occurrence S or O;
• Q2 represents independently for each occurrence O, S, or NR8;
• m is independently for each occurrence an integer in the range 0 to 8 inclusive;
• and
• n is 0 or 1;
• provided that when the geminal instances of R2 and R3 taken together represent O, R7 is not acetyl.

A compound represented by structure 4:

• wherein
• R represents independently for each occurrence hydrogen;
• alkyl;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three are S, O and/or N;
• aralkyl;
• or monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three are S, O and/or N;
• R1 is absent, or present between 1 and 4 times;
• R1 represents independently for each occurrence a halide;
• alkyl;
• alkenyl;
• alkynyl;
• hydroxyl;
• alkoxyl;
• silyloxy;
• amino;
• nitro;
• sulfhydryl;
• —R9SR8;
• —C(R8)═NR8;
• —N═C(R8)2;
• —C(O)N(R8)2;
• —Q2—P(Q1)(OR8)2;
• —Q2—P(Q1)R8(OR8);
• —P(R8)3;
• carboxyl;
• —R9C(O)OC(O)R8;
• silyl;
• —SR8;
• alkylsulfonyl;
• arylsulfonyl;
• —SeR8;
• —R9C(O)R8;
• —R9C(O)H;
• —R9C(O)OR;
• —OC(O)R;
• heteroalkyl;
• —R9CN;
• —R9NHC(═NH)NH2;
• —R9C(═NH)NH2;
• —R9CH(OR8)2;
• —R9C(OR8)2R8;
• —O—N(R8)3;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three ring atoms are selected independently from the group consisting of S, O, and N;
• aralkyl;
• monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three ring atoms are selected independently from the group consisting of S, O, and N;
• —N3;
• —R9CH(NH)CH2;
• —N(R8)C(O)OR8;
• —R9OC(O)N(R8)2;
• —R9CH(O)CH2;
• —R9C(O)N(R8)OH;
• —ON(R8)C(O)R8;
• —R9C(O)N(R8)C(O)R8;
• —N(C(O)R8)2;
• —R9C(R8)═NOH;
• —N(R8)S(O)2R8;
• —C(S)N(R8)2;
• —N(R8)C(S)R8;
• —N(R8)C(O)N(R8)2;
• —N(R8)C(S)N(R8)2;
• or —(CH2)m—R80;
• R2 and R3 represent independently for each occurrence hydrogen;
• alkyl;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three are S, O and/or N;
• aralkyl;
• monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three are S, O and/or N;
• OR;
• N(R)2;
• CO2R;
• C(O)N(R)2;
• OC(O)R;
• or N(R)C(O)R;
• or the geminal instances of R2 and R3 taken together may represent O or C(R)2;
• R6 represents hydrogen;
• alkyl;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three are S, O and/or N;
• aralkyl;
• monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three are S, O and/or N;
• acyl;
• C(O)OR;
• C(O)N(R)2;
• or SO2R;
• R7 represents hydrogen;
• alkyl;
• alkenyl;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three are S, O and/or N;
• aralkyl;
• monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three are S, O and/or N;
• C(O)OR;
• C(O)N(R)2;
• or SO2R;
• R80 represents independently for each occurrence an aryl, cycloalkyl, cycloalkenyl, heterocyclyl, or polycyclyl group comprised of 10 to 20 ring atoms, of which 0 to 6 are S, O and/or N and the remainder carbon;
• R8 represents independently for each occurrence hydrogen, alkyl, alkenyl, alkynyl, or aryl;
• R9 represents independently for each occurrence a bond or an alkyl, alkenyl, alkynyl, or aryl biradical;
• Q1 represents independently for each occurrence S or O;
• Q2 represents independently for each occurrence O, S, or NR8;
• and
• m is independently for each occurrence an integer in the range 0 to 8 inclusive;
• provided that R2 and R3 are not both methyl.

A compound represented by structure 5:

• wherein
• R represents independently for each occurrence hydrogen;
• alkyl;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three are S, O and/or N;
• aralkyl;
• or monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three are S, O and/or N;
• R1 is absent, or present between 1 and 4 times;
• R1 represents independently for each occurrence a halide;
• alkyl;
• alkenyl;
• alkynyl;
• hydroxyl;
• alkoxyl;
• silyloxy;
• amino;
• nitro;
• sulfhydryl;
• —R9SR8;
• —C(R8)═NR8;
• —N═C(R8)2;
• —C(O)N(R8)2;
• —Q2—P(Q1)(OR8)2;
• —Q2—P(Q1)R8(OR8);
• —P(R8)3;
• carboxyl;
• —R9C(O)OC(o)R8;
• silyl;
• —SR8;
• alkylsulfonyl;
• arylsulfonyl;
• —SeR8;
• —R9C(O)R8;
• —R9C(O)H;
• —R9C(O)OR;
• —OC(O)R;
• heteroalkyl;
• —R9CN;
• —R9NHC(═NH)NH2;
• —R9C(═NH)NH2;
• —R9CH(OR8)2;
• —R9C(OR8)2R8;
• —O—N(R8)3;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three ring atoms are selected independently from the group consisting of S, O, and N;
• aralkyl;
• monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three ring atoms are selected independently from the group consisting of S, O, and N;
• —N3;
• —R9CH(NH)CH2;
• —N(R8)C(O)OR8;
• —R9OC(O)N(R8)2;
• —R9CH(O)CH2;
• —R9C(O)N(R8)OH;
• —ON(R8)C(O)R8;
• —R9C(O)N(R8)C(O)R8;
• —N(C(O)R8)2;
• —R9C(R8)═NOH;
• —N(R8)S(O)2R8;
• —C(S)N(R8)2;
• —N(R8)C(S)R8;
• —N(R8)C(O)N(R8)2;
• —N(R8)C(S)N(R8)2;
• or —(CH2)m—R80;
• R2 and R3 represent independently for each occurrence hydrogen;
• alkyl;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three are S, O and/or N;
• aralkyl;
• monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three are S, O and/or N;
• OR;
• N(R)2;
• CO2R;
• C(O)N(R)2;
• OC(O)R;
• or N(R)C(O)R;
• or the geminal instances of R2 and R3 taken together may represent O or C(R)2;
• R6 represents hydrogen;
• alkyl;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three are S, O and/or N;
• aralkyl;
• monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three are S, O and/or N;
• acyl;
• C(O)OR;
• C(O)N(R)2;
• or SO2R;
• R7 represents hydrogen;
• alkyl;
• alkenyl;
• aryl;
• monocyclic or bicyclic heteroaryl with 5-12 ring atoms, of which one to three are S, O and/or N;
• monocyclic or bicyclic heteroaralkyl with 5-12 ring atoms, of which one to three are S, O and/or N;
• acyl;
• C(O)N(R)2;
• or SO2R;
• R80 represents independently for each occurrence an aryl, cycloalkyl, cycloalkenyl, heterocyclyl, or polycyclyl group comprised of 10 to 20 ring atoms, of which 0 to 6 are S, O and/or N and the remainder carbon;
• R8 represents independently for each occurrence hydrogen, alkyl, alkenyl, alkynyl, or aryl;
• R9 represents independently for each occurrence a bond or an alkyl, alkenyl, alkynyl, or aryl biradical;
• Q1 represents independently for each occurrence S or O;
• Q2 represents independently for each occurrence O, S, or NR8;
• and
• m is independently for each occurrence an integer in the range 0 to 8 inclusive.