Camphor-derived compounds, method for manufacturing the same, and application thereof

A method for manufacturing a camphor-derived compound, comprising the following steps:

• (a) providing a compound represented by the following formula (Ia),
• wherein X is O, or S, R3 and R4 independently are C1-10 alkyl, C5-14 cycloalkyl, C4-13 heterocycloalkyl, C6-14 aryl, or C4-13 heteroaryl, wherein the heterocyclo and the heteroaryl have at least one heteroatom selected from the group consisting of O, S, Se, and N, or R3 and R4 are conjugated to form —(CH2)mZ(CH2)n—, wherein m and n are 1, 2, or 3, Z is —CH2—, —NH—, —O—, or —S—;
• and
• (b) forming a compound represented by the following formula (I) from the compound represented by the formula (Ia),
• wherein R1 and R2 independently are —ORa, —SRb, cyano, —CH2NH2, or
• and when R1 is —ORa or SRb, R2 is cyano, —CH2NH2, or
• when R1 is cyano, —CH2NH2, or
• R2 is —ORa or SRb, wherein Ra is H or silyl substituted by one to three C1-10 alkyl, Rb is H or C1-10 alkyl substituted by C6-14 aryl, Rc and Rd independently are C1-10 alkyl, C5-14 cycloalkyl, C4-13 heterocycloalkyl, C6-14 aryl, or C4-13 heteroaryl, wherein the heterocyclo and the heteroaryl have at least one heteroatom selected from the group consisting of O, S, Se, and N, or Rc and Rd are conjugated to form —(CH2)mZ(CH2)n—, wherein m and n are 1, 2, or 3, Z is —CH2—, —NH—, —O—, or —S—;
• or R1 and R2 are combined to form ═O, or ═S.

A method for asymmetric addition of an organic zinc to an aldehyde, comprising the following step:

• reacting R5C(O)H and R6ZnR7 in presence of a catalyst represented by the following formula (I),
• wherein R1 and R2 independently are —ORa, —SRb, cyano, —CH2NH2, or
• and when R1 is —ORa or SRb, R2 is cyano, —C2H2, or
• when R1 is cyano, —CH2NH2, or
• R2 is —ORa or SRb, wherein Ra is H or silyl substituted by one to three C1-10 alkyl, Rb is H or C1-10 alkyl substituted by C6-14 aryl, Rc and Rd independently are C1-10 alkyl, C5-14 cycloalkyl, C4-13 heterocycloalkyl, C6-14 aryl, or C4-13 heteroaryl, wherein the heterocyclo and the heteroaryl have at least one heteroatom selected from the group consisting of O, S, Se, and N, or Rc and Rd are conjugated to form —(CH2)mZ(CH2)n—, wherein m and n are 1, 2, or 3, Z is —CH2—, NH—, —O—, or —S—;
• or R1 and R2 are combined to form ═O, or ═S;
• and
• R3 and R4 independently are C1-10 alkyl, C5-14 cycloalkyl, C4-13 heterocycloalkyl, C6-14 aryl, or C4-13 heteroaryl, wherein the heterocyclo and the heteroaryl have at least one heteroatom selected from the group consisting of O, S, Se, and N, or R3 and R4 are conjugated to form —(CH2)mZ(CH2)n—, wherein m and n are 1, 2, or 3, Z is —CH2—, —NH—, —O—, or —S—;
• and
• R5, R6 and R7 independently are C1-10 alkyl, C2-10 alkenyl, C5-14 cycloalkyl, C4-13 heterocycloalkyl, C5-14 cycloalkenyl, C5-14 heterocycloalkenyl, C6-14 aryl, or C4-13 heteroaryl, wherein the heterocycloalkyl, the heterocycloalkenyl and the heteroaryl have at least one heteroatom selected from the group consisting of O, S, Se, and N, wherein the C1-10 alkyl, the C2-10 alkenyl, the C5-14 cycloalkyl, the C4-13 heterocycloalkyl, the C5-14 cycloalkenyl, the C5-14 heterocycloalkenyl, the C6-14 aryl, or the C4-13 heteroaryl is optionally substituted by C1-10 alkyl, halogen, cyano, —CO2—C1-10 alkyl, —CO2—C2-10 alkenyl, C1-10 haloalkyl, C2-10 alkenyl, C1-10 alkoxyl, C5-14 cycloalkyl, C4-13 heterocycloalkyl, C5-14 cycloalkenyl, C5-14 heterocycloalkenyl, C6-14 aryl, or C4-13 heteroaryl.