Ligand, Method for Producing the Same, and Catalyst Using the Ligand

A ligand represented by following general formula Ia:

• wherein each of R1 and R2 independently represents 0 to 5 substituent groups;
• X represents P, As or N;
• m represents an integer of 0 to 7;
• n represents an integer of 0 to 3;
• and each of A1 to A4 independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a benzoyl group, an acetyl group, a nitro group, a trifluoroacetyl group, a trifluoromethyl group, an alkoxy group represented by —ORa (Ra represents a linear or branched alkyl group having 1 to 4 carbon atoms), an amino group represented by —NRbRc (each of Rb and Rc independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms), a linear or branched alkyl group having 1 to 4 carbon atoms, a hydroxyl group or a ring formed of A2 and A3.

A ligand represented by following general formula Ib:

• wherein each of R1 and R2 independently represents 0 to 5 substituent groups;
• X represents P, As or N;
• m represents an integer of 0 to 7;
• n represents an integer of 0 to 3;
• and each of A1 to A4 independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a benzoyl group, an acetyl group, a nitro group, a trifluoroacetyl group, a trifluoromethyl group, an alkoxy group represented by —ORa (Ra represents a linear or branched alkyl group having 1 to 4 carbon atoms), an amino group represented by —NRbRc (each of Rb and Rc independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms), a linear or branched alkyl group having 1 to 4 carbon atoms, a hydroxyl group or a ring formed of A2 and A3.

A method of producing a ligand represented by following general formula I from a compound represented by following general formula II:

• wherein each of R1 and R2 independently represents 0 to 5 substituent groups;
• X represents P, As or N;
• m represents an integer of 0 to 7;
• n represents an integer of 0 to 3;
• and each of A1 to A4 independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a benzoyl group, an acetyl group, a nitro group, a trifluoroacetyl group, a trifluoromethyl group, an alkoxy group represented by —ORa (Ra represents a linear or branched alkyl group having 1 to 4 carbon atoms), an amino group represented by NRbRc (each of Rb and Rc independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms), a linear or branched alkyl group having 1 to 4 carbon atoms, a hydroxyl group or a ring formed of A2 and A3, and
• wherein R3 represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkenyl group having 2 to 8 carbon atoms, a benzyl group, a paramethoxy benzyl group or a silyl group;
• m has the same definition as described above;
• and each of A1 to A4 independently has the same definition as described above,
• the method comprising the steps of:
• a) reacting the compound represented by the general formula II with a metal salt of diphenylphosphine, diarylphosphine or diarylamine;
• b) thereafter, processing with ammonium chloride and hydrogen peroxide;
• and
• b′) when X is As or N and R3 is one other than a hydrogen atom, allowing palladium-carbon to react with hydrogen, lithium chloride, dichlorodicyanobenzoquinone, cerium ammonium nitrate or a fluorine anion to make the R3 a hydrogen atom, to obtain the ligand represented by the general formula I.

A method of producing a ligand represented by following general formula Ia from a compound represented by following general formula IIa:

• wherein each of R1 and R2 independently represents 0 to 5 substituent groups;
• X represents P, As or N;
• m represents an integer of 0 to 7;
• n represents an integer of 0 to 3;
• and each of A1 to A4 independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a benzoyl group, an acetyl group, a nitro group, a trifluoroacetyl group, a trifluoromethyl group, an alkoxy group represented by —ORa (Ra represents a linear or branched alkyl group having 1 to 4 carbon atoms), an amino group represented by NRbRc (each of Rb and Rc independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms), a linear or branched alkyl group having 1 to 4 carbon atoms, a hydroxyl group or a ring formed of A2 and A3, and
• wherein R3 represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkenyl group having 2 to 8 carbon atoms, a benzyl group, a paramethoxy benzyl group or a silyl group;
• m has the same definition as described above;
• and each of A1 to A4 independently has the same definition as described above,
• the method comprising the steps of:
• a) reacting the compound represented by the general formula Ia with a metal salt of diphenylphosphine, diarylphosphine or diarylamine;
• b) thereafter, processing with ammonium chloride and hydrogen peroxide;
• and
• b′) when X is As or N and R3 is one other than a hydrogen atom, allowing palladium-carbon to react with hydrogen, lithium chloride, dichlorodicyanobenzoquinone, cerium ammonium nitrate or a fluorine anion to make the R3 a hydrogen atom, to obtain the ligand represented by the general formula Ia.

A method of producing a ligand represented by following general formula Ib from a compound represented by following general formula IIb:

• wherein each of R1 and R2 independently represents 0 to 5 substituent groups;
• X represents P, As or N;
• m represents an integer of 0 to 7;
• n represents an integer of 0 to 3;
• and each of A1 to A4 independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a benzoyl group, an acetyl group, a nitro group, a trifluoroacetyl group, a trifluoromethyl group, an alkoxy group represented by —ORa (Ra represents a linear or branched alkyl group having 1 to 4 carbon atoms), an amino group represented by —NRbRc (each of Rb and Rc independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms), a linear or branched alkyl group having 1 to 4 carbon atoms, a hydroxyl group or a ring formed of A2 and A3, and
• wherein R3 represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkenyl group having 2 to 8 carbon atoms, a benzyl group, a paramethoxy benzyl group or a silyl group;
• m has the same definition as described above;
• and each of A1 to A4 independently has the same definition as described above,
• the method comprising the steps of:
• a) reacting the compound represented by the general formula IIb with a metal salt of diphenylphosphine, diarylphosphine or diarylamine;
• b) thereafter, processing with ammonium chloride and hydrogen peroxide;
• and
• b′) when X is As or N and R3 is one other than a hydrogen atom, allowing palladium-carbon to react with hydrogen, lithium chloride, dichlorodicyanobenzoquinone, cerium ammonium nitrate or a fluorine anion to make the R3 a hydrogen atom, to obtain the ligand represented by the general formula Ib.

A producing method of a ligand represented by following general formula I from a compound represented by following general formula II:

• wherein each of R1 and R2 independently represents 0 to S substituent groups;
• X represents P, As or N;
• m represents an integer of 0 to 7;
• n represents an integer of 0 to 3;
• and each of A1 to A4 independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a benzoyl group, an acetyl group, a nitro group, a trifluoroacetyl group, a trifluoromethyl group, an alkoxy group represented by —ORa (Ra represents a linear or branched alkyl group having 1 to 4 carbon atoms), an amino group represented by —NRbRc (each of Rb and Rc independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms), a linear or branched alkyl group having 1 to 4 carbon atoms, a hydroxyl group or a ring formed of A2 and A3, and
• wherein R3 represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkenyl group having 2 to 8 carbon atoms, a benzyl group, a paramethoxy benzyl group or a silyl group;
• m has the same definition as described above;
• and each of A1 to A4 independently has the same definition as described above,
• the method comprising the steps of:
• g) reacting the compound represented by the general formula II with diethylaluminum cyanide, followed by reacting with concentrated hydrochloric acid, to obtain a compound represented by following general formula VII, wherein m, R3 and A1 to A4 have the same definitions as described above;
• h) reacting the compound represented by the general formula VII with a BH3 tetrahydrofuran complex, a BH3 dimethylsulfide complex or LiAlH4, to obtain a compound represented by following general formula VIII, wherein m, R3 and A1 to A4 have the same definitions as described above;
• j) reacting the compound represented by the general formula VIII with p-toluenesulfonyl chloride, to obtain a compound represented by following general formula IX, wherein Ts represents a p-toluenesulfonyl group;
• and m, R3 and A1 to A4 have the same definitions as described above;
• k) reacting the compound represented by the general formula IX with potassium diphenyl phosphide, followed by reacting with hydrogen peroxide, to obtain a compound represented by following general formula X, wherein m, R3 and A1 to A4 have the same definitions as described above;
• and
• l) reacting the compound represented by the general formula X with lithium iodide, to obtain the ligand represented by the general formula I:

A method of producing a ligand represented by following general formula Ia from a compound represented by following general formula IIa:

• wherein each of R1 and R2 independently represents 0 to 5 substituent groups;
• X represents P, As or N;
• m represents an integer of 0 to 7;
• n represents an integer of 0 to 3;
• and each of A1 to A4 independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a benzoyl group, an acetyl group, a nitro group, a trifluoroacetyl group, a trifluoromethyl group, an alkoxy group represented by —ORa (Ra represents a linear or branched alkyl group having 1 to 4 carbon atoms), an amino group represented by —NRbRc (each of Rb and Rc independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms), a linear or branched alkyl group having 1 to 4 carbon atoms, a hydroxyl group or a ring formed of A2 and A3, and
• wherein R3 represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkenyl group having 2 to 8 carbon atoms, a benzyl group, a paramethoxy benzyl group or a silyl group;
• m has the same definition as described above;
• and each of A1 to A4 independently has the same definition as described above,
• the method comprising the steps of:
• g) reacting a compound represented by the general formula IIa with diethylaluminum cyanide, followed by reacting with concentrated hydrochloric acid, to obtain a compound represented by following general formula VIIa, wherein m, R3 and A1 to A4 have the same definitions as described above;
• h) reacting the compound represented by the general formula VIIa with a BH3 tetrahydrofuran complex, a BH3 dimethylsulfide complex or LiAlH4, to obtain a compound represented by following general formula VIIIa, wherein m, R3 and A1 to A4 have the same definitions as described above;
• j) reacting the compound represented by the general formula VIIIa with p-toluenesulfonyl chloride, to obtain a compound represented by following general formula IXa, wherein Ts represents a p-toluenesulfonyl group, and m, R3 and A1 to A4 have the same definitions as described above;
• k) reacting the compound represented by the general formula IXa with potassium diphenyl phosphide, followed by reacting with hydrogen peroxide, to obtain a compound represented by following general formula Xa, wherein m, R3 and A1 to A4 have the same definitions as described above;
• and
• l) reacting the compound represented by the general formula Xa with lithium iodide, to obtain the ligand represented by the general formula Ia:

A method of producing a ligand represented by following general formula Ib from a compound represented by following general formula IIb:

• wherein each of R1 and R2 independently represents 0 to 5 substituent groups;
• X represents P, As or N;
• m represents an integer of 0 to 7;
• n represents an integer of 0 to 3;
• and each of A1 to A4 independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a benzoyl group, an acetyl group, a nitro group, a trifluoroacetyl group, a trifluoromethyl group, an alkoxy group represented by —ORa (Ra represents a linear or branched alkyl group having 1 to 4 carbon atoms), an amino group represented by —NRbRc (each of Rb and Rc independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms), a linear or branched alkyl group having 1 to 4 carbon atoms, a hydroxyl group or a ring formed of A2 and A3, and
• wherein R3 represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkenyl group having 2 to 8 carbon atoms, a benzyl group, a paramethoxy benzyl group or a silyl group;
• m has the same definition as described above;
• and each of A1 to A4 independently has the same definition as described above,
• the method comprising the steps of:
• g) reacting a compound represented by the general formula IIb with diethylaluminum cyanide, followed by reacting with concentrated hydrochloric acid, to obtain a compound represented by following general formula VIIb, wherein m, R3 and A1 to A4 have the same definitions as described above;
• h) reacting the compound represented by the general formula VIIb with a BH3 tetrahydrofuran complex, a BH3 dimethylsulfide complex or LiAlH4, to obtain a compound represented by following general formula VIIb, wherein m, R3 and A1 to A4 have the same definitions as described above;
• j) reacting the compound represented by the general formula VIIb with p-toluenesulfonyl chloride, to obtain a compound represented by following general formula IXb, wherein Ts represents a p-toluenesulfonyl group, and m, R3 and A1 to A4 have the same definitions as described above;
• k) reacting the compound represented by the general formula IXb with potassium diphenyl phosphide, followed by reacting with hydrogen peroxide, to obtain a compound represented by following general formula Xb, wherein m, R3 and A1 to A4 have the same definitions as described above;
• and
• l) reacting the compound represented by the general formula Xb with lithium iodide, to obtain the ligand represented by the general formula Ib:

A catalyst being formed of:

• A) a metal alkoxide or a metal amide represented by Mx(OR4)y or Mx′(NR5)y′, wherein M is a metal selected from the group consisting of titanium, zirconium, aluminum, gallium, barium and rare earth elements;
• each of R4 and R5 independently represents a substituted or non-substituted, linear or branched or cyclic alkyl group having 2 to 6 carbon atoms, a substituted or non-substituted, linear or branched or cyclic alkenyl group, a substituted or non-substituted aromatic group or a trialkylsilyl group, and x and y and x′ and y′ are integers stoichiometrically determined by the metal M;
• and
• B) a ligand represented by following general formula I, wherein each of R1 and R2 independently represents 0 to 5 substituent groups;
• X represents P, As or N;
• m represents an integer of 0 to 7;
• n represents an integer of 0 to 3;
• and each of A1 to A4 independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a benzoyl group, an acetyl group, a nitro group, a trifluoroacetyl group, a trifluoromethyl group, an alkoxy group represented by —ORa (Ra represents a linear or branched alkyl group having 1 to 4 carbon atoms), an amino group represented by —NRbRc (each of Rb and Rc independently represents a hydrogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms), a linear or branched alkyl group having 1 to 4 carbon atoms, a hydroxyl group or a ring formed of A2 and A3: