Phosphine ligands and use thereof in carbonylation of acetylene/ethylene to synthesize acrylate/propionate

A phosphine ligand comprising a structure represented by Formula I, V, or VI,

• wherein the phosphine ligand of Formula I has the following structure:
• wherein
• RI-1 is selected from substituted or unsubstituted C1-10 alkyl, C3-12 cycloalkyl, optionally containing adamantyl, C6-30 aryl;
• RI-2 is selected from the substituted or unsubstituted 5-20 membered heteroaryl;
• RI-3 is selected from hydrogen, substituted or unsubstituted C1-10 alkyl, substituted or unsubstituted C1-10 alkoxy, substituted or unsubstituted C2-10 ester group, cyano, COOH, benzenesulfonyl, trialkylsilyl (wherein said alkyl is C1-4 alkyl), nitro, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted 5-30 membered heteroaryl;
• or two R3 groups attached to adjacent carbon atoms together with the carbon atoms to which they are attached form a group selected from the group consisting of:
• C6-10 aryl, 5-12 membered heteroaryl;
• A is selected from substituted and unsubstituted C1-4 alkyl,
• A and
• are linked to form
• wherein, is the attachment site linked to phosphorus;
• and
• when A is
• then RI-4 is one or more substituents selected from hydrogen, C1-10 alkyl, C1-10 alkoxy, C2-10 ester, cyano, COOH, benzenesulfonyl, tri(C1-4 alkyl)silyl, nitro, C6-30 aryl, and 5-30 membered heteroaryl;
• or RI-4 groups together with RI-3 and adjacent pyridine ring atoms form a fused 5-7 membered carbocyclic or heterocyclic ring;
• when used herein, substituted refers to replacement of one or more hydrogens by radicals independently selected from C1-10 alkyl, C1-10 alkoxy, C2-10 ester, cyano, COOH, phenylsulfonyl, tri(C1-4 alkyl)silyl, nitro, C6-30 aryl, or 5-30 membered heteroaryl, unless expressly stated otherwise;
• wherein the phosphine ligand of Formula V has the following structure:
• wherein
• RV-1 is selected from substituted or unsubstituted C1-12 alkyl, C3-10 cycloalkyl, C6-30 aryl;
• RV-2 is selected from the substituted or unsubstituted 5-20 membered heteroaryl;
• and
• RV-1 is selected from substituted or unsubstituted C1-12 alkyl, C3-10 cycloalkyl;
• RV-2 is selected from the substituted or unsubstituted C6-30 heteroaryl;
• RV-3, RV-4, RV-5, RV-6, RV-7, RV-8, RV-9, RV-10 are independently selected from hydrogen, hydroxyl, halogen, C1-12 alkyl, C3-12 cycloalkyl, C3-10 heterocycloalkyl, C2-10 alkenyl, C6-30 aryl, 5-20 membered heteroaryl, C1-10 alkoxyl, C1-10 alkylamino, C1-10 alkylamino, C1-10 alkylthio;
• two adjacent RV-3, RV-4, RV-5, RV-6, RV-7, RV-8, RV-9, RV-10 located on rings, together with the ring atoms to which they are attached, form a 4-8 membered carbocycle or heterocycle;
• A if it is -L1-A1-L2-, may each independently be selected from chemical bonds, O, NH, S, substituted or unsubstituted C1-12 alkyl, C3-8 cycloalkyl, C3-8 heterocycloalkyl, C6-30 aryl, 5-20 membered heteroaryl, biphenyl,
• with the proviso that L1, A1 and L2 are not all a chemical bond at the same time;
• and
• if the said aryl and heteroaryl are substituted by two or more substituents, any two of said substituents may, together with the ring atoms to which they are attached, form a 4-8 membered carbocycle or heterocycle;
• M is selected from Fe, Co, Ru;
• B is selected from substituted or unsubstituted methylene, ethylidene, ═CHR, ═NR, hydroxymethyl, carbonyl, thiocarbonyl,
• —C(O)—C(O)—;
• where R is selected from substituted or unsubstituted C1-10 alkyl, C6-30 aryl, and 5-20 membered heteroaryl;
• B is selected from substituted or unsubstituted methylene, ethylidene, ═CHR, ═NR, hydroxymethyl, carbonyl, thiocarbonyl,
• —C(O)—C(O)—;
• where R is selected from substituted or unsubstituted C1-10 alkyl, C6-30 aryl, 5-20 membered heteroaryl;
• R11, R12 are independently selected from hedrogen, hydroxyl, substituted or unsubstituted C1-10 alkyl, or
• form 5-8 membered heterocycles, each may be unsubstituted or substituted by C1-6 alkyl;
• X is selected from O, S;
• Z is selected from O, S, NH;
• when used herein, substituted refers to replacement of one or more hydrogens by radicals independently selected from C1-10 alkyl, C1-10 alkoxy, C2-10 ester, cyano, COOH, phenylsulfonyl, tri(C1-4 alkyl)silyl, nitro, C6-30 aryl, or 5-30 membered heteroaryl, benzyl, —CH(Ph)2, unless expressly stated otherwise;
• wherein the phosphine ligand of Formula VI has the following structure:
• wherein
• RVI-1, RVI-4 are independently selected from substituted or unsubstituted C1-10 alkyl, C3-10 cycloalkyl, C6-30 aryl;
• RVI-2, RVI-3 are independently selected from 5-20 membered heteroaryl;
• RVI-5, RVI-6 are independently selected from hydrogen, C1-10 alkyl, C1-10 alkoxy, C2-10 ester, cyano, COOH, benzenesulfonyl, tri(C1-4 alkyl)silyl, nitro, C6-30 aryl, and 5-30 membered heteroaryl;
• two adjacent RVI-5, RVI-6 located on rings, together with the ring atoms to which they are attached, form a 5-7 membered carbocycle or heterocycle;
• wherein the heterocycles contain 1-3 heteroatoms selected from N, O, S;
• when used herein, substituted refers to replacement of one or more hydrogens by radicals independently selected from C1-10 alkyl, C1-10 alkoxy, C2-10 ester, cyano, COOH, phenylsulfonyl, tri(C1-4 alkyl)silyl, nitro, C6-30 aryl, or 5-30 membered heteroaryl, unless expressly stated otherwise.