The present invention refers to processes for catalytic reversible alkene-nitrile interconversion through controllable HCN-free transfer hydrocyanation.

The present invention refers to processes for catalytic reversible alkene-nitrile interconversion through controllable HCN-free transfer hydrocyanation.

A chemoselective and reactive Mn(CF.sub.3-PDP) catalyst system that enables for the first time the strategic advantages of late-stage aliphatic CH hydroxylation to be leveraged in aromatic compounds. This discovery will benefit small molecule therapeutics by enabling the rapid diversification of aromatic drugs and natural products and identification of their metabolites.

A chemoselective and reactive Mn(CF.sub.3-PDP) catalyst system that enables for the first time the strategic advantages of late-stage aliphatic CH hydroxylation to be leveraged in aromatic compounds. This discovery will benefit small molecule therapeutics by enabling the rapid diversification of aromatic drugs and natural products and identification of their metabolites.

According to one aspect, a process of forming a diisocyanate compound from limonene is disclosed. The process includes performing an oxidation reaction to form a limonene-ketone from limonene having a ketone group at a first position. The process includes performing a conjugate addition reaction on the limonene-ketone to form a limonene-nitrile having a nitrile group bonded at a second position. The process also includes performing a reductive amination reaction on the limonene-nitrile to form a limonene-diamine by reducing the nitrile group to form a first amine group and converting the ketone group to a second amine group. The process further includes forming the diisocyanate compound by converting the first amine group of the limonene-diamine to a first isocyanate group and the second amine group of the limonene-diamine to a second isocyanate group.

According to one aspect, a process of forming a diisocyanate compound from limonene is disclosed. The process includes performing an oxidation reaction to form a limonene-ketone from limonene having a ketone group at a first position. The process includes performing a conjugate addition reaction on the limonene-ketone to form a limonene-nitrile having a nitrile group bonded at a second position. The process also includes performing a reductive amination reaction on the limonene-nitrile to form a limonene-diamine by reducing the nitrile group to form a first amine group and converting the ketone group to a second amine group. The process further includes forming the diisocyanate compound by converting the first amine group of the limonene-diamine to a first isocyanate group and the second amine group of the limonene-diamine to a second isocyanate group.

According to one aspect, a process of forming a diisocyanate compound from limonene is disclosed. The process includes performing an oxidation reaction to form a limonene-ketone from limonene having a ketone group at a first position. The process includes performing a conjugate addition reaction on the limonene-ketone to form a limonene-nitrile having a nitrile group bonded at a second position. The process also includes performing a reductive amination reaction on the limonene-nitrile to form a limonene-diamine by reducing the nitrile group to form a first amine group and converting the ketone group to a second amine group. The process further includes forming the diisocyanate compound by converting the first amine group of the limonene-diamine to a first isocyanate group and the second amine group of the limonene-diamine to a second isocyanate group.

According to one aspect, a process of forming a diisocyanate compound from limonene is disclosed. The process includes performing an oxidation reaction to form a limonene-ketone from limonene having a ketone group at a first position. The process includes performing a conjugate addition reaction on the limonene-ketone to form a limonene-nitrile having a nitrile group bonded at a second position. The process also includes performing a reductive amination reaction on the limonene-nitrile to form a limonene-diamine by reducing the nitrile group to form a first amine group and converting the ketone group to a second amine group. The process further includes forming the diisocyanate compound by converting the first amine group of the limonene-diamine to a first isocyanate group and the second amine group of the limonene-diamine to a second isocyanate group.

The present disclosure features a strain-promoted [2+2+2] reaction that can be carried out under physiological conditions. In general, the reaction involves reacting a pi-electrophile with a low lying LUMO with a quadricyclane on a biomolecule, generating a covalently modified biomolecule. The selectivity of the reaction and its compatibility with aqueous environments provides for its application in vivo and in vitro. The reaction is compatible with modification of living cells. In certain embodiments, the pi-electrophile can comprise a molecule of interest that is desired for delivery to a quadricyclane-containing biomolecule via [2+2+2] reaction.

The present disclosure features a strain-promoted [2+2+2] reaction that can be carried out under physiological conditions. In general, the reaction involves reacting a pi-electrophile with a low lying LUMO with a quadricyclane on a biomolecule, generating a covalently modified biomolecule. The selectivity of the reaction and its compatibility with aqueous environments provides for its application in vivo and in vitro. The reaction is compatible with modification of living cells. In certain embodiments, the pi-electrophile can comprise a molecule of interest that is desired for delivery to a quadricyclane-containing biomolecule via [2+2+2] reaction.