Chiral phosphoramidimidates and derivatives thereof

A chiral phosphoramidimidate having the general formula (I):

• or a tautomeric and/or ionic form thereof,
• wherein:
• X represents O, S, Se or NRN,
• Z1 to Z4 may be, independently from each other, the same or different and represent O, S, Se and NRN,
• n stands for 0 or 1,
• W is selected from hydrogen, halogen, a metal selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Mo, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt, Au, Al, Pb, La, Sm, Eu, Yb, or U, or a cationic organic group, or a substituted silicon —SiRIRIIRIII, wherein RI, RII and RIII are the same or different and each stands for hydrogen, halogen, C1 to C20 straight chain, branched chain or cyclic aliphatic hydrocarbon, C3-C8-heterocycloalkyl, C6 to C20 aromatic hydrocarbon or a partially arene-hydrogenated form thereof, aryl-(C1-C6)-alkyl, or heteroaryl-(C1-C6)-alkyl, each said aliphatic hydrocarbon, heterocycloalkyl, aromatic hydrocarbon or partially arene-hydrogenated form thereof, arylalkyl, or heteroaryl-alkyl optionally being substituted on a hydrocarbyl portion thereof by one or more groups selected from C1 to C20 straight chain, branched chain or cyclic aliphatic hydrocarbons, optionally having one or more unsaturated bonds, C3-C8-heterocycloalkyl, C6 to C20 aromatic hydrocarbons or partially arene-hydrogenated forms thereof, aryl-(C1-C6)-alkyl, heteroaryl-(C1-C6)-alkyl, or heterosubstituents,
• R1, R2, R3 and R4 may be, independently from each other, the same or different and are each an aliphatic, heteroaliphatic, aromatic or heteroaromatic hydrocarbon group, each optionally being further substituted by one or more heterosubstituents, or aliphatic, heteroaliphatic, aromatic or heteroaromatic hydrocarbon groups,
• whereby R1 may form a ring system with any one of R2, R3 or R4 and the other two of R2, R3 or R4 may form a ring system with each other;
• and
• RN is an electron withdrawing group, being the same or different on each N and being selected from:
• i. -alkyl, —CO-alkyl, —(CO)—O-alkyl, sulfinyl alkyl, sulfonyl alkyl, or —(P═O)-dialkyl, wherein alkyl is a C1 to C20 straight chain, branched chain or cyclic aliphatic hydrocarbon having at least one halogen substituent on the alkyl residue;
• ii. aryl, —CO-aryl, —(CO)—O-aryl, sulfinyl aryl, sulfonyl aryl, or —(P═O)-diaryl, wherein aryl is a C6 to C18 aromatic hydrocarbon, optionally having at least one halogen substituent on the aryl residue;
• iii. heteroaryl, —CO-heteroaryl, —(CO)—O-heteroaryl, sulfinyl heteroaryl, sulfonyl heteroaryl, or —(P═O)-di-heteroaryl, wherein heteroaryl is a C2 to C20 aromatic hydrocarbon having one or more heteroatoms, and wherein the heteroaryl optionally has at least one halogen substituent on the heteroaryl residue;
• or
• in the case that X represents NRN, one RN may be bridging the two P═N— units to form a ring represented by formula:
• wherein RN1 represents —(SO)—, —(SO2)— or —(NRN2)— wherein RN2 is an electron withdrawing group being selected from -alkyl, —CO-alkyl, or —(CO)—O-alkyl, wherein alkyl is a C1 to C20 straight chain, branched chain or cyclic aliphatic hydrocarbon having at least one halogen substituent on the alkyl residue.

A chiral phosphoramidimidate having the general formula (I):

• or a tautomeric and/or ionic form thereof,
• wherein:
• X represents O, S, Se or NRN,
• Z1 to Z4 are, independently from each other, the same or different and represent O, S, Se or NRN,
• n stands for 0 or 1,
• W is selected from hydrogen, halogen, a metal selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Mo, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt, Au, Al, Pb, La, Sm, Eu, Yb, or U, or a cationic organic group, or a substituted silicon —SiRIRIIRIII, wherein RI, RII and RIII are the same or different and each stands for hydrogen, halogen, C1 to C20 straight chain, branched chain or cyclic aliphatic hydrocarbon, C3-C8-heterocycloalkyl, C6 to C20 aromatic hydrocarbon or a partially arene-hydrogenated form thereof, aryl-(C1-C6)-alkyl, or heteroaryl-(C1-C6)-alkyl, each said aliphatic hydrocarbon, heterocycloalkyl, aromatic hydrocarbon or partially arene-hydrogenated form thereof, arylalkyl, or heteroaryl-alkyl optionally being substituted on a hydrocarbyl portion thereof by one or more groups selected from C1 to C20 straight chain, branched chain or cyclic aliphatic hydrocarbons, optionally having one or more unsaturated bonds, C3-C8-heterocycloalkyl, C6 to C20 aromatic hydrocarbons or partially arene-hydrogenated forms thereof, aryl-(C1-C6)-alkyl, heteroaryl-(C1-C6)-alkyl, or heterosubstituents,
• R1, R2, R3 and R4 are, independently from each other, the same or different and are each an aliphatic, heteroaliphatic, aromatic or heteroaromatic hydrocarbon group, each optionally being further substituted by one or more heterosubstituents, or aliphatic, heteroaliphatic, aromatic or heteroaromatic hydrocarbon groups,
• whereby R1 may form a ring system with any one of R2, R3 or R4 and the other two of R2, R3 or R4 may form a ring system with each other;
• and
• RN is an electron withdrawing group, being the same or different on each N and being selected from:
• i. sulfinyl alkyl, or sulfonyl alkyl, wherein alkyl is a C1 to C20 straight chain, branched chain or cyclic aliphatic hydrocarbon having at least one halogen substituent on the alkyl residue;
• ii. sulfinyl aryl, or sulfonyl aryl, wherein aryl is a C6 to C18 aromatic hydrocarbon having at least one halogen substituent on the aryl residue;
• iii. sulfinyl heteroaryl, or sulfonyl heteroaryl, wherein heteroaryl is a C2 to C20 aromatic hydrocarbon having one or more heteroatoms, and wherein the heteroaryl has at least one halogen substituent on the heteroaryl residue;
• or
• in the case that X represents NRN, one RN may be bridging the two P═N— units to form a ring represented by formula:
• wherein RN1 represents —(SO)—, —(SO2)— or —(NRN2)— wherein RN2 is an electron withdrawing group being selected from -alkyl, —CO-alkyl, or —(CO)—O-alkyl, wherein alkyl is a C1 to C20 straight chain, branched chain or cyclic aliphatic hydrocarbon having at least one halogen substituent on the alkyl residue.