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US 12,441,669 B2Granted
PCNHCP metal complexes and uses thereof
AssigneeTechnion Research & Development Foundation Limited
InventorsGraham De Ruiter, Subhash Garhwal
Life of this patent
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Abstract
PCNHCP pincer metal complexes are useful as catalysts in various chemical reactions such as hydrogen isotope exchange (HIE) in C(sp3)-H and/or C(sp2)-H bond of an organic compound, e.g., a pharmaceutically active compound. The complexes are also useful in hydroboration of alkynes with excellent selectivity; and alkene isomerization with high stereo- and regioselectivity.
Claims35
A metal complex of formula I:
- wherein:
- R1, R2, R3, and R4 each independently is selected from the group consisting of (C1-C18)alkyl, (C2-C18)alkenyl, (C3-C7)cycloalkyl, —O—(C1-C18)alkyl, (C3-C12)heterocyclyl, a 6-14-membered aryl, and a 5-10-membered heteroaryl;
- or R1 and R2, and/or R3 and R4, together with the phosphorus atom to which they are attached form a heterocyclic ring optionally containing one or more heteroatoms selected from the group consisting of O, N, and S;
- R5, R6, R7, R8, R9, and R10 each independently is selected from the group consisting of H, (C1-C18)alkyl, (C2-C18)alkenyl, (C3-C7)cycloalkyl, (C3-C12)heterocyclyl, a 6-14-membered aryl, a 5-10-membered heteroaryl, —CF3, —OR, —SR, and —NRR′, or any two of adjacent R5, R6, R7, R8, R9, and R10 together with the carbon atoms to which they are attached form a 5-14-membered ring optionally containing one or more heteroatoms selected from the group consisting of O, N, and S;
- M is an earth-abundant metal having an oxidation state selected from the group consisting of −2, −1, 0, +1, +2, +3, +4, +5, and +6;
- X, Y and Z each independently is selected from the group consisting of H, deuterium (D), tritium (T), N2, CO, NO, N2O, (C1-C18)alkyl, (C2-C18)alkenyl, (C3-C7)cycloalkyl, —O—(C1-C18)alkyl, (C3-C12)heterocyclyl, a 6-14-membered aryl, a 5-10-membered heteroaryl, halogen, azide (N3−), cyanide (CN−), cyanate (OCN−), isocyanide (RNC), isocyanate (RNCO), thiocyanate (SCN−), isothiocyanate (RNCS), sulfide (S2−), oxo (O2−), peroxo (R—O—O), hydroperoxo (H—O—O−), superoxide (O2−), —NRR′, —SR, and a coordinating solvent;
- or one of X, Y and Z is selected from the group consisting of H, D and T, and the other two of X, Y and Z form a bidentate ligand;
- R and R′ each independently is selected from the group consisting of H, (C1-C18)alkyl, (C2-C18)alkenyl, (C3-C7)cycloalkyl, (C3-C12)heterocyclyl, a 6-14-membered aryl, a 5-10-membered heteroaryl, and a trialkylsilyl;
- Q is an optional counter ion;
- and
- the asterisk represents an optional net charge of said metal complex which depends on the oxidation state of said metal and the groups X, Y and Z,
- provided that at least one of X, Y and Z each independently is selected from the group consisting of H, D, and T.
9 more elements
A metal complex of formula II:
- wherein:
- R1, R2, R3, and R4 each independently is selected from the group consisting of (C1-C18)alkyl, (C2-C18)alkenyl, (C3-C7)cycloalkyl, —O—(C1-C18)alkyl, (C3-C12)heterocyclyl, a 6-14-membered aryl, and a 5-10 membered heteroaryl;
- or R1 and R2, and/or R3 and R4, together with the phosphorus atom to which they are attached form a heterocyclic ring optionally containing one or more heteroatoms selected from the group consisting of O, N, or and S;
- R5, R6, R7, R8, R9, and R10 each independently is selected from the group consisting of H, (C1-C18)alkyl, (C2-C18)alkenyl, (C3-C7)cycloalkyl, (C3-C12)heterocyclyl, a 6-14-membered aryl, a 5-10-membered heteroaryl, —CF3, —OR, —SR, and —NRR′, or any two of adjacent R5, R6, R7, R8, R9, and R10 together with the carbon atoms to which they are attached form a 5-14-membered ring optionally containing one or more heteroatoms each independently selected from the group consisting of O, N or and S;
- M is an earth-abundant metal having an oxidation state selected from the group consisting of −2, −1, 0, +1, +2, +3, +4, +5, and +6;
- X and Y each independently is selected from the group consisting of H, deuterium (D), tritium (T), N2, CO, NO, N2O, (C1-C18)alkyl, (C2-C18)alkenyl, (C3-C7)cycloalkyl, —O—(C1-C18)alkyl, (C3-C12)heterocyclyl, a 6-14-membered aryl, a 5-10-membered heteroaryl, halogen, azide (N3−), cyanide (CN−), cyanate (OCN−), isocyanide (RNC), isocyanate (RNCO), thiocyanate (SCN−), isothiocyanate (RNCS), sulfide (S2−), oxo (O2−), peroxo (R—O—O), hydroperoxo (H—O—O−), superoxide (O2−), —NRR′, —SR, and a coordinating solvent;
- or X and Y form a bidentate ligand;
- R and R′ each independently is selected from the group consisting of H, (C1-C18)alkyl, (C2-C18)alkenyl, (C3-C7)cycloalkyl, (C3-C12)heterocyclyl, a 6-14-membered aryl, a 5-10-membered heteroaryl, and a trialkylsilyl;
- Q is an optional counter ion;
- and
- the asterisk represents an optional net charge of said metal complex which depends on the oxidation state of said metal and the groups X and Y.
8 more elements
Dependencies are inferred from the claim text.