Synthetic transtaganolide and basiliolide products, derivatives thereof, and synthesis methods thereof

A method of synthesizing a compound represented by Formula I, comprising:

• reacting a compound represented by Formula II with a compound represented by Formula III,
• wherein:
• Y is selected from —OR9, —N, R10, R11, —SR12, wherein R9, R10, R11, and R12 are each independently selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
• M is selected from Li, Na, hydrogen, SiR13R14R15, snR16R17R18, BR19R20, ZnX2, MgX2, wherein R13, R14, R15, R16, R17, and R18 are each independently selected from hydrocarbyl or substituted hydrocarbyl, R19 and R20 are each independently selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl, and X is any halogen;
• W is selected from —O, —S, or —NR21, wherein R21 is hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
• Z is selected from —O, —S, or —NR22, wherein R22 is hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
• R1, R2, and R3 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
• R4, R5, and R6 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
• and
• R7 and R8 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl, wherein two or more adjacent R groups optionally combine to form a ring.

A method of enriching for an enantiomer of Formula I, comprising:

• synthesizing a compound of Formula III in which one of R7′ and R8′ is a silyl group and the other of R7′ and R8′ is hydrogen;
• removing the silyl group to form an enantioselective compound;
• and
• reacting a compound of Formula II with the enantioselective Formula III compound, to form the compound of Formula I.
• wherein:
• Y is selected from —OR9, —N, R10, R11, —SR12, wherein R9, R10, R11, and R12 are each independently selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
• M is selected from Li, Na, hydrogen, SiR13R14R15, SnR16R17R18, BR19R20, ZnX2, and MgX2, wherein R13, R14, R15, R16, R17, and R18 are each independently selected from hydrocarbyl and substituted hydrocarbyl, R19 and R20 are each independently selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl, and X is any halogen;
• W is selected from —O, —S, or —NR21, wherein R21 is hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
• Z is selected from —O, —S, or —NR22, wherein R22 is hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
• R1, R2, and R3 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl;
• and
• R4, R5, and R6 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;
• and
• any two or more adjacent R groups optionally combine to form a ring.

A compound, comprising a synthetic compound represented by Formula IV:

• wherein:
• Ra is selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl;
• Wa is selected from the group consisting of —ORx, —SRxx, and —NRxxxRxxxx, where each of Rx, Rxx, Rxxx and Rxxxx is independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl;
• each of R3 through R8 is selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl;
• Z is selected from the group consisting of —O, —S and —NR22, wherein R22 is selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl;
• any two or more of Ra and R3 through R8 optionally combine to form a ring.

A method of synthesizing a compound of Formula IV, the method comprising reacting a compound of Formula IV-I with a compound of Formula IV-II according to reaction scheme 11 to form the compound of Formula IV:

• wherein:
• Ra is selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl;
• Wa is selected from the group consisting of —ORx,—SRxx, and —NRxxxRxxxx, where each of Rx, Rxx, Rxxx and Rxxxx is independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl;
• each of R3 through R8 is selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl;
• Z is selected from the group consisting of —O, —S and —NR22, wherein R22 is selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl;
• M is selected from the group consisting of Li, Na, hydrogen, SiR12R14R15, SnR16R17R18, BR19R20, MgX′2 and ZnX″2, wherein:
• each of R13 through R18 is independently selected from the group consisting of hydrocarbyl, and substituted hydrocarbyl,
• each of R19 and R20 is independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl, and
• each of X′ and X″ is independently selected from the group consisting of halogens;
• X is a halogen;
• and
• any two or more of Ra and R3 through R8 optionally combine to form a ring.