Tunable chiral monophosphines as ligands in enantioselective rhodium-catalyzed ring-opening of oxabenzonorbornadienes with amines

A new tunable chiral monophosphine was used as a ligand for asymmetric rhodium-catalyzed ring-opening of oxabenzonorbornadiene with amines, providing a series of chiral ring-opened products in high yields (up to 97%) and with high enantioselectivities (>99%).The reaction can be performed at rt to obtain the desired product with high enantioselectivity.

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(1R,2R)-2-(4-Phenylpiperazin-1-yl)-1,2-dihydronaphthalen-1-olC20H22N2O[α]D27 = −158.9 (c 0.53, CHCl3)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

(1R,2R)-2-(4-(2-Methoxyphenylpiperazin-1-yl)-1,2-dihydronaphthalen-1-olC21H24N2O2[α]D27 = −131.8 (c 0.57, CHCl3)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

(1R,2R)-2-(4-o-Tolylpiperazin-1-yl)-1,2-dihydronaphthalen-1-olC21H24N2O[α]D27 = −122.2 (c 0.37, CHCl3)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

(1R,2R)-2-(4-(2-Fluorophenyl)piperazin-1-yl)-1,2-dihydronaphthalen-1-olC20H21FN2O[α]D27 = −154.7 (c 0.67, CHCl3)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

(1R,2R)-2-(4-(3-Chlorophenyl)piperazin-1-yl)-1,2-dihydronaphthalen-1-olC20H21ClN2O[α]D27 = −153.7 (c 0.43, CHCl3)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

(1R,2R)-2-(4-p-Tolylpiperazin-1-yl)-1,2-dihydronaphthalen-1-olC21H24N2O[α]D27 = −120.9 (c 0.38, CHCl3)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

(1R,2R)-2-(4-(4-Methoxyphenyl)piperazin-1-yl)-1,2-dihydronaphthalen-1-olC21H24N2O2[α]D27 = −162.5 (c 0.43, CHCl3)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

(1R,2R)-2-(4-(4-(Trifluoromethyl)phenylpiperazin-1-yl)-1,2-dihydronaphthalen-1-olC21H21F3N2O[α]D27 = −161.9 (c 0.45, CHCl3)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

(1R,2R)-2-(4-(2,4-Dimethylphenyl)piperazin-1-yl)-1,2-dihydronaphthalen-1-olC22H26N2O[α]D27 = −160.8 (c 0.55, CHCl3)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

(1R,2R)-2-(4-(3,4-Dichlorophenyl)piperazin-1-yl)-1,2-dihydronaphthalen-1-olC20H20Cl2N2O[α]D27 = −130.95 (c 0.37, CHCl3)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

(1R,2R)-2-(4-(3-Chlorobenzyl)piperazin-1-yl)-1,2-dihydronaphthalen-1-olC21H23ClN2O[α]D27 = −146.0 (c 0.68, CHCl3)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

tert-Butyl 4-((1R,2R)-1-hydroxy-1,2-dihydronaph-thalen-2-yl) piperazine-1-carboxylateC19H26N2O3[α]D27 = −111.05 (c 0.46, CHCl3)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

(1R,2R)-6,7-Difluoro-2-(4-phenylpiperazin-1-yl)-1,2-dihydronaphthalen-1-olC20H20F2N2O[α]D27 = −72.55 (c 0.28, CHCl3)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

(1R,2R)-6,7-Difluoro-2-(4-(2-fluorophenyl)piperazin-1-yl)-1,2-dihydronaphthalen-1-olC20H19F3N2O[α]D27 = −113.0 (c 0.73, CHCl3)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

(1R,2R)-6,7-Difluoro-2-(4-(2-methoxyphenyl)piperazin-1-yl)-1,2-dihydronaphth-alen-1-olC21H22F2N2O2[α]D27 = −110.0 (c 0.68, CHCl3)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

(1R,2R)-6,7-Difluoro-2-(4-p-tolylpiperazin-1-yl)-1,2-dihydronaphthalen-1-olC21H22F2N2O[α]D27 = −115.55 (c 0.38, CHCl3)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

(1R,2R)-6,7-Difluoro-2-(4-(4-methoxyphenyl)-piperazin-1-yl)-1,2-dihydronaphth-alen-1-olC21H22F2N2O2[α]D27 = −113.9 (c 0.89, CHCl3)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

(1R,2R)-2-(4-(3,4-Dichlorophenyl)piperazin-1-yl)-6,7-difuoro-1,2-dihydronaphthalen-1-olC20H18Cl2F2N2O[α]D27 = −117.5 (c 0.39, CHCl3)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

(1R,2R)-2-(4-(2,4-Dimethylphenyl)piperazin-1-yl)-6,7-difluoro-1,2-dihydronaphthalen-1-olC22H24F2N2O[α]D27 = −129.3 (c 0.94, CHCl3)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

(1R,2R)-6,7-Dimethoxy-2-(4-phenylpiperazin-1-yl)-1,2-dihydronaphthalen-1-olC22H26N2O3[α]D27 = −225.3 (c 0.62, CHCl3)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

(1R,2R)-6,7-Dimethoxy-2-(4-(2-methoxyphenyl)-piperazin-1-yl)-1,2-dihydronaphthalen-1-olC23H28N2O4[α]D27 = −199.4 (c 0.82, CHCl3)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

(1R,2R)-6,7-Dimethoxy-2-(4-(4-(trifluoromethyl)-phenyl)piperazin-1-yl)-1,2-dihydronaphthalen-1-olC23H25F3N2O3[α]D27 = −198.4 (c 1.23, CHCl3)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

(1R,2R)-6,7-Dimethoxy-2-(4-(4-methoxyphenyl)-piperazin-1-yl)-1,2-dihydronaphthalen-1-olC23H28N2O4[α]D27 = −204.2 (c 1.12, CHCl3)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

(1R,2R)-2-(Phenylamino)-1,2-dihydronaphthalen-1-olC16H15NO[α]D27 = −138.4 (c 0.32, CH2Cl2)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

(1R,2R)-2-[Methyl(phenyl)amino]-1,2-dihydronaphthalen-1-olC17H17NO[α]D27 = −112.9 (c 0.72, CH2Cl2)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

(1R,2R)-2-((3-Chlorophenyl)(methyl)amino)-1,2-dihydronaphthalen-1-olC17H16ClNO[α]D27 = −143.7 (c 0.92, CH2Cl2)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

(1R,2R)-2-((4-Chlorophenyl)(methyl)amino)-1,2-dihydronaphthalen-1-olC17H16ClNO[α]D27 = −112.0 (c 0.82, CH2Cl2)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

(1R,2R)-2-(Methyl(p-tolyl)amino)-1,2-dihydronaphthalen-1-olC18H19NO[α]D27 = −132.3 (c 0.62, CH2Cl2)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

(1R,2R)-2-(Ethyl(phenyl)amino)-1,2-dihydronaphthalen-1-olC18H19NO[α]D27 = −160.7 (c 0.85, CH2Cl2)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

(1R,2R)-2-(Allyl(methyl)amino)-1,2-dihydronaphthalen-1-olC14H17NO[α]D27 = −83.4 (c 0.28, CH2Cl2)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

(1R,2R)-2-(3,4-Dihydroisoquinolin-2(1H)-yl)-1,2-dihydronaphthalen-1-olC19H19NO[α]D27 = −134.9 (c 0.82, CH2Cl2)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)

(1R,2R)-2-(Benzyl(methyl)amino)-1,2-dihydronaphthalen-1-olC18H19NO[α]D27 = −118.2 (c 0.32, CH2Cl2)Source of chirality: asymmetric catalysisAbsolute configuration: (1R,2R)