A pineno-salen type catalyst for the enantioselective Nozaki–Hiyama–Kishi reaction

A new class of pineno-salen type ligands 10, 11, 17, 20, 23, and 24 has been developed. The catalyst formed from chromium(II)-10 promotes the enantioselective Nozaki–Hiyama–Kishi allylation of alkyl and aryl aldehydes using allyl bromide. Notably, the asymmetric addition of vinyl halide to benzaldehyde was achieved with 24% ee.

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(1S,8S,9R)-10,10-Dimethyl-5-phenyl-6-aza-tricyclo[7.1.1.02,7]undeca-2(7),3,5-trien-8-ylamineC18H20N2[α]D25=+118.2 (c 1.0, CHCl3)Absolute configuration: (1S,8S,9R)Source of chirality: (IR)-(+)-α-pinene

(1S,8R,9R)-10,10-Dimethyl-5-phenyl-6-aza-tricyclo[7.1.1.02,7]undeca-2(7),3,5-trien-8-ylamineC18H20N2[α]D25=+22.0 (c 1.0, CHCl3)Absolute configuration: (1S,8R,9R)Source of chirality: (IR)-(+)-α-pinene

(1S,8S,9R)-2,4-Di-tert-butyl-6-[(10,10-dimethyl-5-phenyl-6-aza-tricyclo[7.1.1.02,7]undeca-2(7),3,5-trien-8-ylimino)-methyl]-phenolC33H40N2O[α]D26=+177.1 (c 0.21, CH2Cl2)Absolute configuration: (1S,8S,9R)Source of chirality: (IR)-(+)-α-pinene

(1S,8R,9R)-2,4-Di-tert-butyl-6-[(10,10-dimethyl-5-phenyl-6-aza-tricyclo[7.1.1.02,7]undeca-2(7),3,5-trien-8-ylimino)-methyl]-phenolC33H40N2O[α]D26=-163.1 (c 0.5, CH2Cl2)Absolute configuration: (1S,8R,9R)Source of chirality: (IR)-(+)-α-pinene

(1S,8S,9R)-2-{8-[(3,5-Di-tert-butyl-2-hydroxy-benzylidene)-amino]-10,10-dimethyl-6-aza-tricyclo[7.1.1.02,7]undeca-2(7),3,5-trien-5-yl}-pyridin-3-olC33H40N2O2[α]D26=+188.0 (c 0.56, CH2Cl2)Absolute configuration: (1S,8S,9R)Source of chirality: (IR)-(+)-α-pinene

(1S,8S,9R)-2,4-Di-tert-butyl-6-[(10,10-dimethyl-5-pyridin-2-yl-6-aza-tricyclo[7.1.1.02,7]undeca-2(7),3,5-trien-8-ylimino)-methyl]-phenolC32H39N3O[α]D23=+126.0 (c 0.27, CH2Cl2)Absolute configuration: (1S,8S,9R)Source of chirality: (IR)-(+)-α-pinene

(1S,8S,9R)-2,4-Di-tert-butyl-6-{[5-(1-methoxy-1-methyl-ethyl)-10,10-dimethyl-6-aza-tricyclo[7.1.1.02,7]undeca-2(7),3,5-trien-8-ylimino]-methyl}-phenolC31H44N2O2[α]D24=+1.0 (c 1.00, CH2Cl2)Absolute configuration: (1S,8S,9R)Source of chirality: (IR)-(+)-α-pinene

(1S,9S)-5-(2-Methoxy-phenyl)-10,10-dimethyl-6-aza-tricyclo[7.1.1.02,7]undeca-2(7),3,5-trieneC19H21NO[α]D23.4=+71.0 (c 1.03, CHCl3)Absolute configuration: (1S,9S)Source of chirality: (IR)-(+)-α-pinene

(1S,8S,9R)-2-[(10,10-Dimethyl-5-phenyl-6-aza-tricyclo[7.1.1.02,7]undeca-2(7),3,5-trien-8-ylimino)-methyl]-phenolC25H24N2O[α]D24.1=+209.0 (c 0.13, CH2Cl2)Absolute configuration: (1S,8S,9R)Source of chirality: (IR)-(+)-α-pinene

(1S,8S,9R)-2-[(10,10-Dimethyl-5-phenyl-6-aza-tricyclo[7.1.1.02,7]undeca-2(7),3,5-trien-8-ylimino)-methyl]-6-methyl-phenolC26H26N2O[α]D24=+225.0 (c 0.25, CH2Cl2)Absolute configuration: (1S,8S,9R)Source of chirality: (IR)-(+)-α-pinene