Synthesis of resveratrol-based natural products

A process for making a compound having the structure:

• wherein R1, R2, R4, R5, R52 and R54 are, independently, H, OH, OMe or
• wherein each of R47, R48, R49, R50, and R51 are, independently, H, OH, alkyl, alkenyl, alkynyl, —OR61, —SR62, —N(R63)2, —S(O)(O)R64, —C(O)OR65, —R66OR67, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, or X,
• where X is a halogen, where R61, R62, R64, R65, R67, and each occurrence of R63, are, independently, H, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, and where R66 is alkylene, alkenylene or alkynylene,
• wherein each occurrence of alkyl, alkenyl, alkynyl, alkylene, alkenylene, and alkynylene is substituted or unsubstituted,
• R3 is H, ═O, —OH, X, —SR69, —N(R70)2,
• where X is a halogen, and where R68, R69 and each occurrence of R70 are, independently, alkyl, alkenyl, or alkynyl,
• wherein each occurrence of alkyl, alkenyl, or alkynyl, is substituted or unsubstituted, and
• where bond a is present or absent,
• the process comprising:
• a) contacting a compound having the structure:
• wherein R52 and R54 are defined as above, R6, R7, R8, R53, R55, R56, R57, and R58, are, independently, H, OH, alkyl, alkenyl, alkynyl, —OR71, —SR72, —N(R73)2, —S(O)(O)R74, —C(O)OR75, —R76OR77, —R76R77, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, or —X,
• where X is a halogen, and where R71, R72, R74, R75, R77 and each occurrence of R73 are, independently, H, alkyl, alkenyl, alkynyl cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, and where R76 is alkylene, alkenylene or alkynylene,
• wherein each occurrence of alkyl, alkenyl, alkynyl, alkylene, alkenylene, and alkynylene is substituted or unsubstituted,
• with an organolithium reagent;
• b) contacting the product of step a) with a substituted benzaldehyde so as to form a compound having the structure:
• wherein R6, R7, R8, R52, R53, R54, R55, R57 and R58 are defined as above, R48 is OH, R9, R10, R11, R59, and R60, are, independently, H, OH, alkyl, alkenyl, alkynyl, —OR78, —SR79, —N(R80)2, —S(O)(O)R81, —C(O)OR82, —R83OR84, —R83R84, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, or —X,
• where X is a halogen, and where R78, R79, R81, R82, R84 and each occurrence of R80 are, independently, H, alkyl, alkenyl, or alkynyl, and where R83 is alkylene, alkenylene or alkynylene,
• wherein each occurrence of alkyl, alkenyl, alkynyl, alkylene, alkenylene, and alkynylene is substituted or unsubstituted;
• and
• c) contacting the product of step b) with an organic acid so as to produce the compound;
• or
• a process for making a compound having the structure
• wherein
• R34, R35, R42, R43, and R106 are, independently, H, OH, OMe, OC(O)R186, or
• wherein each of R114, R115, R116, R117, and R118 are, independently, H, OH, —OC(O)alkyl, alkyl, alkenyl, alkynyl, —OR107, —SR108, —N(R109)2, —S(O)(O) R110, —C(O)OR111, —R112OR113, —R112R113, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, or X,
• where X is a halogen, where R107, R108, R110, R111, R113, and each occurrence of R109, are, independently, H, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, and where R112 is alkylene, alkenylene or alkynylene,
• wherein each occurrence of alkyl, alkenyl, alkynyl, alkylene, alkenylene, and alkynylene is substituted or unsubstituted,
• wherein R186 is alkyl or alkenyl
• wherein R36, R37, R38, R39 and R40 are, independently, H, OH, —OC(O)alkyl, alkyl, alkenyl, alkynyl, —OR114, —SR115, —N(R116)2, —S(O)(O)R117, —C(O)OR118, —R119OR120, —R119R120, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, or X,
• where X is a halogen, where R114, R115, R117, R118, R120, and each occurrence of R116, are, independently, H, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, and where R119 is alkylene, alkenylene or alkynylene,
• wherein each occurrence of alkyl, alkenyl, alkynyl, alkylene, alkenylene, and alkynylene is substituted or unsubstituted,
• or R40 is joined to R41 to form a pentacyclic ring,
• bond β is present, each of bond χ, bond δ, bond κ, R45 and R46 are absent, R44 is present, and R41 is O,
• or
• bond β is absent, bond κ is absent, bond δ is present, R45 is present, bond χ and R46 are absent, R44 is present, and R41 is —OC(O)(CF3), —OH, -alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl,
• OR120, —N(R122)2, or —R′Y;
• or
• wherein each occurrence of alkyl, alkenyl, alkynyl, alkylene, alkenylene, and alkynylene is substituted or unsubstituted,
• bond β is absent, bond κ is present, bond δ is absent, R44 and R45 are absent, bond χ and R46 are absent, and R41 is a halogen, —OH,
• X, OR120, —SR121, —N(R122)2, or —R′Y,
• where R120, R121 and each occurrence of R122 are alkyl, alkenyl or alkynyl, and where R′ is alkylene, alkenylene or alkynylene and Y is cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl;
• or
• wherein each occurrence of alkyl, alkenyl, alkynyl, alkylene, alkenylene, and alkynylene is substituted or unsubstituted,
• bond β is absent, bond κ is absent, each of bond δ, bond χ, R44, R45 and R46 are present, and R41 is joined to R40 to form a pentacyclic ring,
• R44, if present, is H,
• R45, if present, is H or Br,
• R46, if present, is
• cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, wherein R46 is only present if R41 is joined to R40 to form a pentacyclic ring,
• R106 is H,
• wherein bond η is present or absent, but when present bond κ is absent,
• comprising the step of reacting a compound having the structure:
• wherein R161 and R166 are OMe or OAc, R162 is Br and R165 and R163 are OMe or OAc and R164 is H or R165 and R163 are H and R164 is OMe or OAc,
• with n-BuLi and a compound having the structure:
• wherein R167 is H or OMe, R168 is H or OMe, and R169 is H or OMe, so as to produce the compound.

A process for making a compound having the structure:

• wherein R23 and R27 are, independently, H or X,
• wherein R16, R17, R18, R19, R20, R21, R22, R24, R25, R26, R28, R29, R30, R31, R32, R33, R135, R136, R137, R138, R139, R140, R141, R142, R143, R144, R145, R146, R147, R148, R149, R150, R151, R152, R153 are, independently, H, OH, alkyl, alkenyl, alkynyl, —OR154, —SR155, —N (R156)2, —S(O)(O) R157, —C(O)OR158, —R155OR160, —R159R160, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, or —X,
• where X is a halogen, and where R154, R155, R157, R158, R160 and each occurrence of R156 are, independently, H, alkyl, alkenyl, or alkynyl, and where R159 is alkylene, alkenylene or alkynylene,
• wherein each occurrence of alkyl, alkenyl, alkynyl, alkylene, alkenylene, and alkynylene is substituted or unsubstituted,
• comprising contacting a compound having the structure:
• wherein R12 and R13 are, independently,
• and R221 is H or —OMe,
• with bromine in a first suitable solvent so as to produce the compound;
• or
• a process for making a compound having the structure:
• wherein R6, R7, R8, R9, R10, R11, R52, R53, R54, R55, R57, R58, R59, R60 are, independently, H, OH, —OMe, —OAc, alkyl, alkenyl, alkynyl, —OR78, —SR79, —N(R80)2, −5(O)(O)R81, —C(O)OR82, —R83OR84, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, or —X,
• where X is a halogen, and where R78, R79, R81, R82, R84 and each occurrence of R80 are, independently, H, alkyl, alkenyl, or alkynyl, and where R83 is alkylene, alkenylene or alkynylene, and
• wherein each occurrence of alkyl, alkenyl, alkynyl, alkylene, alkenylene, and alkynylene is substituted or unsubstituted
• R48 is H, ═O, OH, —OAc, —OMe,
• comprising reacting a compound having the structure:
• wherein R176, R177, R178, R179, R180, R181, R182, R183, R184, R185 are, independently, H, Br, or OMe, with n-BuLi and a compound having the structure:
• wherein R167 is H, OAc or OMe, R168 is H, OAc or OMe, and R169 is H, OAc or OMe, so as to produce the compound;
• or
• a process for making a compound having the structure:
• comprising:
• a) reacting a compound having the structure:
• with NaBH4 and PBR3 to produce a compound having the structure:
• b) reacting the product of step a) with NBS in a suitable solvent;
• c) reacting the product of step b) with KHMDS and HP(O)(OEt)2 so as to produce the compound;
• or
• a process for making a compound having the structure:
• wherein R161 and R166 are OMe or OAc, R162 is Br and R164 and R163 are OMe or OAc and R165 is H comprising:
• a) contacting a compound having the structure:
• with KOt-Bu;
• and
• b) reacting the product of step a) with 3,4-dimethoxybenzaldehyde so as to obtain the compound.

The process for making a compound having the structure:

• wherein R123, R124, R125, R126, and R127, are, independently, H, OH, —OMe, alkyl, alkenyl, alkynyl, —OR128, —SR129, —N(R130)2, —S(O)(O)R131, —C(O)OR132, —R133OR134, R133R134, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, or —X,
• where X is a halogen, and where R128, R129, R131, R132, R134 and each occurrence of R130 are, independently, H, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, and where R133 is alkylene, alkenylene or alkynylene,
• wherein each occurrence of alkyl, alkenyl, alkynyl, alkylene, alkenylene, and alkynylene is substituted or unsubstituted,
• the process comprising contacting a compound having the structure:
• wherein R6, R7, R8, R52, R53, R54, R55, R57 and R58 are defined as above, R48 is OH, R9, R10, R11, R59, and R60, are, independently, H, OH, alkyl, alkenyl, alkynyl, —OR78, —SR79, —N(R80)2, —S(O)(O)R81, —C(O)OR82, —R83OR84, —R83R84, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, or —X,
• where X is a halogen, and where R78, R79, R81, R82, R84 and each occurrence of R80 are, independently, H, alkyl, alkenyl, or alkynyl, and where R83 is alkylene, alkenylene or alkynylene,
• wherein each occurrence of alkyl, alkenyl, alkynyl, alkylene, alkenylene, and alkynylene is substituted or unsubstituted,
• with a metal catalyst so as to make the compound;
• or
• a process for making a compound having the structure
• wherein R14, R15, R188, R187, R188, R189, R190, R191, are, independently, ═O, H, OH, —OC(O)alkyl, alkyl, alkenyl, alkynyl, —OR212, —SR213, —N(R214)2, —S(O)(O)R215, —C(O)OR216, —R217OR218, —R217R218, —SO2—R219, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, or X,
• where X is a halogen, where R212, R213, R215, R216, R218, R219, and each occurrence of R214, are, independently, H, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, and where R217 is alkylene, alkenylene or alkynylene,
• wherein each occurrence of alkyl, alkenyl, alkynyl, alkylene, alkenylene, and alkynylene is substituted or unsubstituted, and wherein bonds φ, λ, and μ are present or absent, but wherein when bond φ is present bond μ is absent, and wherein when bond μ is present bond φ is absent, comprising:
• a) reacting a compound having the structure:
• with an oxidizing agent so as to obtain a compound having the structure:
• wherein R220 is H or —OMe, and
• b) contacting the product of step a) with a dioxirane, an acid, or Br2 so as to obtain the compound;
• or
• a process for making a compound having the structure:
• comprising the step of reacting a compound having the structure:
• wherein R161 and R166 are OMe, R162 is Br and
• R165 and R163 are H and R164 is OMe,
• with n-BuLi and a compound having the structure:
• wherein R167 is OMe, R168 is H, and R169 is OMe, so as to produce the compound;
• or
• a process for making a compound having the structure:
• wherein R192, R192, R193, R194, R195, R196, R197, R199, R199, R200, R201, R202, and R203 are, independently, H, OH, Br, —OMe, —OAc,
• and wherein R204 is H, OH, ═O, Br, —OAc, —OMe, and wherein bond ν is present when R204 is ═O, comprising the step of reacting a compound having the structure:
• wherein R161 and R166 are OMe or OAc, R162 is Br and
• R164 and R163 are OMe or OAc and R165 is H or R165 and R163 are H and R164 is OMe or OAc,
• with n-BuLi and a compound having the structure:
• wherein R167 is H or OMe or OAc, R168 is H or OMe or OAc, and R169 is H or OMe or OAc, so as to produce the compound.

A compound having the structure:

• wherein R14, R15, R188, R187, R188, R189, R190, R191, are, independently, ═O, H, OH, —OC(O)alkyl, alkyl, alkenyl, alkynyl, —OR212, —SR213, —N(R214)2, —S(O)(O) R215, —C(O)OR216, —R217OR218 —R217R218, —SO2 —R219 cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, or X,
• where X is a halogen, where R212, R213, R215, R216, R218, R219, and each occurrence of R214, are, independently, H, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, and where R217 is alkylene, alkenylene or alkynylene,
• wherein each occurrence of alkyl, alkenyl, alkynyl, alkylene, alkenylene, and alkynylene is substituted or unsubstituted,
• wherein bonds φ, ξ, λ, and μ are present or absent, but wherein when bond φ is present bonds ξ and μ are absent, and wherein when bond μ is present bond φ is absent, and wherein when bond ξ is present bond φ is absent;
• or
• wherein R192, R192, R193, R194, R195, R196, R197, R198, R199, R200, R201, R202, and R203 are, independently, H, OH, ═O, —OC(O)alkyl, alkyl, alkenyl, alkynyl, —OR205, —SR206, —N(R207)2, —S(O)(O)R208, —C(O)OR209, —R210OR211, —R210R211 cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, or X,
• where X is a halogen, where R205, R206, R208, R209, R211, and each occurrence of R207, are, independently, H, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted- or unsubstituted heterocyclyl, and where R210 is alkylene, alkenylene or alkynylene,
• wherein each occurrence of alkyl, alkenyl, alkynyl, alkylene, alkenylene, and alkynylene is substituted or unsubstituted
• and wherein bond ν is present or absent;
• or
• wherein R3, R6, R7, R8, R52, R53, R54, R55, and R58 are defined as above, R9, R10, R11, and R59, are, independently, H, OH, alkyl, alkenyl, alkynyl, —OR78, —SR79, —N(R80)2, —S(O)(O)R81, —C(O)OR82, —R83OR84, —R83R84, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, or —X,
• where X is a halogen, and where R78, R79, R81, R82, R84 and each occurrence of R80 are, independently, H, alkyl, alkenyl, or alkynyl, and where R83 is alkylene, alkenylene or alkynylene,
• wherein each occurrence of alkyl, alkenyl, alkynyl, alkylene, alkenylene, and alkynylene is substituted or unsubstituted.

A compound having the structure:

• wherein R6, R7, R8, R52, R53, R54, R55, R57 and R58 are defined as above, R48 is OH, R9, R10, R11, R59, and R60, are, independently, H, OH, alkyl, alkenyl, alkynyl, —OR78, SR79, —N(R80)2, —S(O)(O)R81, —C(O)OR82, —R83OR84, —R83R84, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, or —X,
• where X is a halogen, and where R78, R79, R81, R82, R84 and each occurrence of R80 are, independently, H, alkyl, alkenyl, or alkynyl, and where R83 is alkylene, alkenylene or alkynylene, and
• wherein each occurrence of alkyl, alkenyl, alkynyl, alkylene, alkenylene, and alkynylene is substituted or unsubstituted;
• or
• wherein
• bond β is absent, R170 and R172 are —OMe, R171 and R174 are, and R175 is —P(O)(OEt)(OEt), R173 is Br, or
• bond β is present, R170, R171, R172, R173 and R174 are, independently, H or OMe;
• or
• wherein R176, R177, R178, R179, R180, R181, R182, R183, R184, R185 are, independently, H, Br, or OMe;
• or
• wherein R6, R7, R8, R9, R10, R11, R52, R53, R54, R55, R57, R58, R59, R60 are, independently, H, OH, —OMe, —OAc, alkyl, alkenyl, alkynyl, —OR78, —SR79, —N(R60)2, —S(O)(O)R81, —C(O)OR82, —R83OR84, —R83R84, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, or —X,
• where X is a halogen, and where R78, R81, R82, R84 and each occurrence of R80 are, independently, H, alkyl, alkenyl, or alkynyl, and where R83 is alkylene, alkenylene or alkynylene, and
• wherein each occurrence of alkyl, alkenyl, alkynyl, alkylene, alkenylene, and alkynylene is substituted or unsubstituted
• R48 is H, ═O, OH, —OAc, —OMe,
• wherein R176, R177, R178, R179, R180, R181, R182, R183, R184, R185 are, independently, H, Br, OH, OAc, or OMe,
• wherein when R185 and R177 are OMe, R176, R178, R179, R180, R182, R183, R184, are H and R178 is Br, then R181 is Br, OH, H or OMe;
• or
• wherein R1, R2, R3, R4, R5, R52, R54, R55, R56, R57 are defined as above.

A composition, free of plant extract, comprising a compound having the structure:

• wherein
• R34, R35, R42, R43, and R106 are, independently, H, OH, OMe or
• wherein each of R114, R115, R116, R117, and R118 are, independently, H, OH, alkyl, alkenyl, alkynyl, —OR107, —SR108, —N(R109)2, —S(O)(O)R110, —C(O)OR111, —R112OR113, —R112R113, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, or X,
• where X is a halogen, where R107, R108, R110, R111, R113, and each occurrence of R109, are, independently, H, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, and where R112 is alkylene, alkenylene or alkynylene,
• wherein each occurrence of alkyl, alkenyl, alkynyl, alkylene, alkenylene, and alkynylene is substituted or unsubstituted,
• wherein R36, R37, R38, R39 and R40 are, independently, H, OH, alkyl, alkenyl, alkynyl, —OR114, —N(R116)2, —S(O)(O)R117, —C(O)OR118, —R119OR120 —R119R120 cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, or X,
• where X is a halogen, where R114, R115, R117, R118, R120, and each occurrence of R116, are, independently, H, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, and where R119 is alkylene, alkenylene or alkynylene,
• wherein each occurrence of alkyl, alkenyl, alkynyl, alkylene, alkenylene, and alkynylene is substituted or unsubstituted,
• or R40 is joined to R41 to form a pentacyclic ring,
• bond β is present, each of bond χ, bond δ, bond κ, R45 and R46 are absent, R44 is present, and R41 is O,
• or
• bond β is absent, bond κ is absent, bond δ is present, R45 is present, bond χ and R46 are absent, R44 is present, and R41 is —OC(O)(CF3), —OH, -alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl,
• X, OR120, —SR121, —N(R122)2, or —R′Y;
• or
• wherein each occurrence of alkyl, alkenyl, alkynyl, alkylene, alkenylene, and alkynylene is substituted or unsubstituted,
• bond β is absent, bond κ is present, bond δ is absent, R44 and R45 are absent, bond χ and R46 are absent, and R41 is H, —OH,
• X, OR120, —SR121, —N(R122)2, or —R′Y,
• where R120, R121 and each occurrence of R122 are alkyl, alkenyl or alkynyl, and where R′ is alkylene, alkenylene or alkynylene and Y is cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl;
• or
• wherein each occurrence of alkyl, alkenyl, alkynyl, alkylene, alkenylene, and alkynylene is substituted or unsubstituted,
• bond β is absent, bond κ is absent, each of bond δ, bond χ, R44, R45 and R46 are present, and R41 is joined to R40 to form a pentacyclic ring,
• R44, if present, is H,
• R45, if present, is H or Br,
• R46, if present, is
• cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl,
• R106 is H,
• wherein when R34 and R43 are OH, R35 is
• , R36, R38, R40, R42 and R44 are H, R37 and R39 are OH, and bond β is present, then R41 is O or
• or
• wherein R14 is ═O, OH, OAc or
• and R15 is
• or Br;
• or
• wherein R6, R7, R8, R52, R53, R54, R55, R57 and R58 are defined as above, R48 is OH, R9, R10, R11, R59, and R60, are, independently, H, OH, alkyl, alkenyl, alkynyl, —OR78, —SR79, —N(R80)2, —S(O)(O)R81, —C(O)OR82, —R83OR84, —R83R84, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, or —X,
• where X is a halogen, and where R78, R79, R81, R82, R84 and each occurrence of R80 are, independently, H, alkyl, alkenyl, or alkynyl, and where R83 is alkylene, alkenylene or alkynylene, and
• wherein each occurrence of alkyl, alkenyl, alkynyl, alkylene, alkenylene, and alkynylene is substituted or unsubstituted;
• or
• wherein
• R34, R35, R42, R43, and R106 are, independently, H, OH, OMe, OC(O)R186 or
• wherein each of R114, R115, R116, R117, and R118 are, independently, H, OH, —OC(O)alkyl, alkyl, alkenyl, alkynyl, OR107 SR108—N (R109)2 —S(O)(O)R110, —C(O)OR111, —R112OR113, —R112R113 cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, or X,
• where X is a halogen, where R107, R108, R110, R111, R113, and each occurrence of R109, are, independently, H, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, and where R112 is alkylene, alkenylene or alkynylene,
• wherein each occurrence of alkyl, alkenyl, alkynyl, alkylene, alkenylene, and alkynylene is substituted or unsubstituted,
• wherein R186 is alkyl or alkenyl
• wherein R36, R37, R38, R39 and R40 are, independently, H, OH, —OC(O)alkyl, alkyl, alkenyl, alkynyl, —OR114, —SR115, —N(R116)2, —S(O)(O)R117, —C(O)OR118, —R119OR120, —R119R120, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, or X,
• where X is a halogen, where R114, R115, R117, R118, R120, and each occurrence of R116, are, independently, H, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, and where R119 is alkylene, alkenylene or alkynylene,
• wherein each occurrence of alkyl, alkenyl, alkynyl, alkylene, alkenylene, and alkynylene is substituted or unsubstituted,
• or R40 is joined to R41 to form a pentacyclic ring,
• bond β is present, each of bond χ, bond δ, bond κ, R45 and R46 are absent, R44 is present, and R41 is O,
• or
• bond β is absent, bond κ is absent, bond δ is present, R45 is present, bond χ and R46 are absent, R44 is present, and R41 is —OC(O)(CF3), —OH, -alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl,
• X,
• OR120, —SR121, —N(R122)2, or —R′Y;
• or
• wherein each occurrence of alkyl, alkenyl, alkynyl, alkylene, alkenylene, and alkynylene is substituted or unsubstituted,
• bond β is absent, bond κ is present, bond δ is absent, R44 and R45 are absent, bond χ and R46 are absent, and R41 is a halogen, —OH,
• X, OR120 —SR121, —N(R122)2, or —R′Y,
• where R120, R121 and each occurrence of R122 are alkyl, alkenyl or alkynyl, and where R′ is alkylene, alkenylene or alkynylene and Y is cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl;
• or
• wherein each occurrence of alkyl, alkenyl, alkynyl, alkylene, alkenylene, and alkynylene is substituted or unsubstituted,
• bond β is absent, bond κ is absent, each of bond δ, bond χ, R44, R45 and R46 are present, and R41 is joined to R40 to form a pentacyclic ring,
• R44, if present, is H,
• R45, if present, is H or Br,
• R46, if present, is
• cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, wherein R46 is only present if R41 is joined to R40 to form a pentacyclic ring,
• R106 is H,
• wherein when R34 and R43 are OH, R35 is
• , R36, R38, R40, R42 and R44 are H, R37 and R39 are OH, and bond β is present, then R41 is O or
• and when R40 is joined to R41 to form a pentacyclic ring, and
• R34 and R43 are OH, R35 and R46 are
• , R36, R38, R42 and R44 are H, R37 and R39 are OH, then R45 is Br.
• Wherein bond η is present or absent, but when present bond κ is absent;
• or
• wherein R14, R15, R188, R187, R188, R189, R190, R191 are, independently, ═O, H, OH, —OC(O)alkyl, alkyl, alkenyl, alkynyl, —OR212, —SR213, —N(R214)2, —S(O)(O)R215, —C(O)OR216, —R217OR218, —R217R218, —SO2 —R219 cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, or X,
• where X is a halogen, where R212, R213, R215, R216, R218, R219, and each occurrence of R214, are, independently, H, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, and where R217 is alkylene, alkenylene or alkynylene,
• wherein each occurrence of alkyl, alkenyl, alkynyl, alkylene, alkenylene, and alkynylene is substituted or unsubstituted,
• wherein bonds φ, ξ, λ, and μ are present or absent, but wherein when bond φ is present bonds ξ and μ are absent, and wherein when bond μ is present bond φ is absent, and wherein when bond ξ is present bond φ is absent;
• or
• wherein R6, R7, R8, R9, R10, R11, R52, R53, R54, R55, R57, R58, R59, R60 are, independently, H, OH, —OMe, —OAc, alkyl, alkenyl, alkynyl, —OR78, —SR79, —N(R80)2, —S(O)(O)R81, —C(O)OR82, —R83OR84, —R83R64, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, or —X,
• where X is a halogen, and where R78, R79, R81, R82, R84 and each occurrence of R80 are, independently, H, alkyl, alkenyl, or alkynyl, and where R83 is alkylene, alkenylene or alkynylene, and
• wherein each occurrence of alkyl, alkenyl, alkynyl, alkylene, alkenylene, and alkynylene is substituted or unsubstituted
• R48 is H, ═O, OH, —OAc, —OMe,
• wherein R192, R192, R193, R194, R195, R196, R197, R198, R199, R200, R201, R202, and R203 are, independently, H, OH, Br, —OMe, —
• and wherein R204 is H, OH, ═O, Br, —OAc, —OMe,
• and wherein bond ν is present when R204 is ═O;
• or
• a compound having the structure:
• wherein R3, R6, R7, R8, R52, R53, R54, R55, and R58 are defined as above, R9, R10, R11, and R59, are, independently, H, OH, alkyl, alkenyl, alkynyl, —OR78, —N(R80)2, —S(O)(O)R81, —C(O)OR82, —R83OR84, —R83R84, cycloalkyl, cycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, or —X,
• where X is a halogen, and where R78, R79, R81, R82, R84 and each occurrence of R80 are, independently, H, alkyl, alkenyl, or alkynyl, and where R83 is alkylene, alkenylene or alkynylene,
• wherein each occurrence of alkyl, alkenyl, alkynyl, alkylene, alkenylene, and alkynylene is substituted or unsubstituted;
• or