Iridium-catalyzed highly enantioselective ring opening reaction of oxabenzonorbornadienes with amines

The complex of [Ir(COD)Cl]2 and (R)-xylyl-phanephos was used as an effective catalyst for the asymmetric ring opening reaction of oxabenzonorbornadienes with various amines. Under the optimized reaction conditions, high enantioselectivities with moderate to good yields could be obtained from a wild scope of oxabenzonorbornadienes and amines.

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(1R,2R)-2-(Methyl(phenyl)amino)-1,2-dihydronaphthalen-1-olC17H17NOee: 96% (HPLC, Chiralcel OD-H)[α]D22 = +31.5 (c 0.34, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2R)

(1R,2R)-2-(Ethyl(phenyl)amino)-1,2-dihydronaphthalen-1-olC18H19NOee: 97% (HPLC, Chiralcel OD-H)[α]D22 = −16.7 (c 0.502, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2R)

(1R,2R)-2-(Isopropyl(phenyl)amino)-1,2-dihydronaphtha-len-1-olC19H21NOee: 96% (HPLC, Chiralcel OD-H)[α]D22 = −66.3 (c 0.228, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2R)

(1R,2R)-2-((4-Bromophenyl)(methyl)amino)-1,2-dihydronaphthalen-1-olC17H16BrNOee: 95% (HPLC, Chiralcel AD-H)[α]D22 = +75.4 (c 0.130, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2R)

(1R,2R)-2-((4-Methoxyphenyl)(methyl)amino)-1,2-dihydronaphthalen-1-olC18H19NO2ee: 97% (HPLC, Chiralcel OD-H)[α]D22 = +21.5 (c 0.0744, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2R)

(1R,2R)-2-(Methyl(naphthalen-2-yl)amino)-1,2-dihydronaphthalen-1-olC21H19NOee: 97% (HPLC, Chiralcel OD-H)[α]D22 = +48.5 (c 0.109, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2R)

(1R,2R)-2-(Dibenzylamino)-1,2-dihydronaphthalen-1-olC24H23NOee: 88% (HPLC, Chiralcel OD-H)[α]D22 = −68.8 (c 0.247, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2R)

(1R,2R)-2-(4-Phenylpiperazin-1-yl)-1,2-dihydronaphtha-len-1-olC20H22N2Oee: 84% (HPLC, Chiralcel OD-H)[α]D22 = −107.6 (c 0.341, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2R)

(1R,2R)-2-(Phenylamino)-1,2-dihydronaphthalen-1-olC16H15NOee: 92% (HPLC, Chiralcel AD-H)[α]D22 = −68.8 (c 0.032, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2R)

(1R,2R)-2-(p-Tolylamino)-1,2-dihydronaphthalen-1-olC17H17NOee: 90% (HPLC, Chiralcel AD-H)[α]D22 = −100.4 (c 0.243, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2R)

(1R,2R)-2-((4-Methoxyphenyl)amino)-1,2-dihydronaphthalen-1-olC17H17NO2ee: 89% (HPLC, Chiralcel AD-H)[α]D22 = −80.3 (c 0.0648, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2R)

(1R,2R)-2-((3-Bromophenyl)amino)-1,2-dihydronaphthalen-1-olC16H14BrNOee: 94% (HPLC, Chiralcel AD-H)[α]D22 = −75.5 (c 0.11, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2R)

(1R,2R)-2-((4-Bromophenyl)amino)-1,2-dihydronaphthalen-1-olC16H14BrNOee: 96% (HPLC, Chiralcel AD-H)[α]D22 = −70.5 (c 0.095, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2R)

(1R,2R)-6,7-Dimethyl-2-(methyl(phenyl)amino)-1,2-dihydronaphthalen-1-olC19H21NOee:97% (HPLC, Chiralcel OD-H)[α]D22 = +18.3 (c 0.278, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2R)

(5R,6R)-6-(Methyl(phenyl)amino)-5,6-dihydronaphtho[2,3-d][1,3]dioxol-5-olC18H17NO3ee:98% (HPLC, Chiralcel OD-H)[α]D22 = +11.6 (c 0.0865, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2R)

(1R,2R)-6,7-Dibromo-2-(methyl(phenyl)amino)-1,2-dihydronaphthalen-1-olC17H15Br2NOee:86% (HPLC, Chiralcel OD-H)[α]D22 = +50.7 (c 0.412, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2R)

(1R,2R)-5,8-Dimethyl-2-(methyl(phenyl)amino)-1,2-dihydronaphthalen-1-olC19H21NOee:98% (HPLC, Chiralcel OD-H)[α]D22 = −334 (c 0.628, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2R)

(1R,2R)-5,8-Dimethoxy-2-(methyl(phenyl)amino)-1,2-dihydronaphthalen-1-olC19H21NO3ee: 97% (HPLC, Chiralcel AD-H)[α]D22 = −156.5 (c 0.20, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2R)