Organoboron derivatives and process for coupling organic compounds

A process for covalently coupling organic compounds which comprises:

• (i) reacting an olefinic compound having at least one carbon to carbon double bond or an acetylenic compound having at least one carbon to carbon triple bond with a diboron derivative in the presence of a Group 8-11 metal catalyst to form an organoboron intermediate having an organoboronate residue on at least one carbon atom of the respective double or triple bond;
• wherein said reaction of the olefinic or acetylenic compound with the diboron derivative is an addition reaction across the double or triple bond respectively, or, in the case of two or more conjugated carbon to carbon double bonds, the reaction introduces organoboronate residues on distal carbon atoms participating in the conjugation, resulting in loss of conjugation, or, in the case of an α,β-unsaturated carbonyl compound, the reaction introduces a single organoboronate residue on the β-carbon, resulting in loss of α,β-unsaturation,
• (ii) adding water, water and a suitable base, or a mild oxidising agent, to decompose excess diboron derivative, and
• (iii) reacting the organoboron intermediate with an organic compound having a halogen or halogen-like substituent at a coupling position in the presence of a Group 8-11 metal catalyst and a suitable base, whereby the olefinic or acetylenic compound is coupled to the organic compound via a direct bond between the carbon atom having the organoboronate residue and the coupling position.

Organoboron compounds selected from the group consisting of:

• 2-[(Z)-2-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-1,2-diphenylethenyl]-5,5-dimethyl-1,3,2-dioxaborinane,
• 2-[(Z)-2-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-1-ethyl-1-butenyl]-5,5-dimethyl-1,3,2-dioxaborinane,
• 2-[(Z)-2-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-1-phenyl-1-butenyl]-5,5-dimethyl-1,3,2-dioxaborinane,
• methyl (Z)-2,3-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-nonenoate,
• (E)4-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3-buten-2-one,
• (Z)-4-phenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3-buten-2-one,
• 2-[(E)-1-(1-cyclohexen-1-yl)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane,
• 1-[(E)-1,2-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethenyl]cyclohexanol,
• (E)-N,N-dimethyl-2,3-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-propen-1-amine,
• (E)-3-ethyl-1,2-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1-penten-3-amine,
• (E)-N,N-di(2-propynyl)-2,3-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-propen-1-amine,
• 4,4-dimethyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)cyclohexanone,
• 4,4,5,5-tetramethyl-2-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-cyclohexen-1yl]-1,3,2-dioxaborolane,
• (Z)-1,5-diphenyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1-penten-3-one,
• 3-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propanal,
• 4,4,5,5-tetramethyl-2-[8-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,4,6-cyclooctatrien-1-yl]-1,3,2-dioxaborolane,
• 4,4,5,5-tetramethyl-2-[6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,4,7-cyclooctatrien-1-yl]-1,3,2-dioxaborolane,
• 4,4,5,5-tetramethyl-2-[8-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-4-cycloocten-1-yl]-1,3,2-dioxaborolane,
• 4,4,5,5-tetramethyl-2-[9-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)tricyclo[5.2.1.02,6]dec-3-en-8-yl]-1,3,2-dioxaborolane,
• 4,4,5,5-tetramethyl-2-[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)tricyclo[5.2.1.02,6]dec-8-en-4-yl]-1,3,2-dioxaborolane,
• 4,4,5,5-tetramethyl-2-(4-methylcyclohexyl)-1,3,2-dioxaborolane,
• 4,4,5,5-tetramethyl-2-(3-methylcyclohexyl)-1,3,2-dioxaborolane,
• 4,4,5,5-tetramethyl-2-[(E)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1-octen-7-ynyl]-1,3,2-dioxaborolane,
• 4,4,5,5-tetramethyl-2-[(1E,7E)-2,7,8-tris(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,7-octadienyl]-1,3,2-dioxaborolane,
• 2-[(Z)-1-butyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1-octen-3-ynyl]4,4,5,5-tetramethyl-1,3,2-dioxaborolane,
• 2-[(1Z,3Z)-1-butyl-2,3,4-tris(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3-octadienyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane,
• 2-[(Z)-2-(4H-1,3,2-benzodioxaborinin-2-yl)-1,2-diphenylethenyl]-4H-1,3,2-benzodioxaborinine,
• 2-[(Z)-1,2-diphenyl-2-(4,4,6-trimethyl-1,3,2-dioxaborinan-2-yl)ethenyl]-4,4,6-trimethyl-1,3,2-dioxaborinane,
• 2-[(Z)-2-(5,5-diethyl-1,3,2-dioxaborinan-2-yl)-1,2-diphenylethenyl]-5,5-diethyl-1,3,2-dioxaborinane,
• (2-{(Z)-2-[4-(phenoxymethyl)-1,3,2-dioxaborolan-2-yl]-1,2-diphenylethenyl}-1,3,2-dioxaborolan-4-yl)methyl phenyl ether,
• (1S,2S,6R,8S)-4-{(Z)-1,2-diphenyl-2-[(1R,2R,6S,8S)-2,9,9-trimethyl-3,5-dioxa-4-boratricyclo[6.1.1.02,6]dec-4-yl]ethenyl}-2,9,9-trimethyl-3,5-dioxa4-boratricyclo[6.1.1.02,6]decane,
• (3aR,6aS)-2-{(Z)-2-[(3aR,6aS)tetrahydro-3aH-cyclopenta[d][1,3,2]dioxaborol-2-yl]-1,2-diphenylethenyl}tetrahydro-3aH-cyclopenta[d][1,3,2]dioxaborole,
• (3aR,6aS)-2-{(Z)-2-[(3aR,6aS)tetrahydrofuro[3,4-d][1,3,2]dioxaborol-2-yl]-1,2-diphenylethenyl}tetrahydrofuro[3,4-d][1,3,2]dioxaborole,
• 2-[(Z)-1,2-diphenyl-2-(4-phenyl-1,3,2-dioxaborolan-2-yl)ethenyl]-4-phenyl-1,3,2-dioxaborolane, and
• (3aR,7aS)-2-{(Z)-2-[(3aR,7aS)hexahydro-1,3,2-bexzodioxaborol-2-yl]-1,2-diphenylethenyl}hexahydro-1,3,2-benzodioxaborole.