Rhodium-Catalyzed Ring-Opening Reactions of N-Boc-azabenzonor­bornadiene with Chiral Amine Nucleophiles Derived from Amino Acids

Abstract

The rhodium-catalyzed ring-opening of azabenzonorbornadienes with chiral amino nucleophiles derived from amino ­acids such as (S)-proline and (R)-phenylglycine is reported. The desired products were obtained as a mixture of diastereomers, which could be easily separated in high yield. Enantiomerically pure ring-fused nitrogen heterocycles and 1,2-diamines were also obtained by further transformation of the ring-opened products.

Key words

rhodium - ring-opening - diamines - heterocycles - diastereoselective

References

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19

For the preparation of 15.0 g of the ring-opened product 3 from 8.0 g of the starting material 1, 2.7 g of (S,S′)-(R,R′)-C₂-Ferriphos would be required to ensure high enantio-selectivity in the catalytic ring-opening reaction.

22

To a solution of (S)-proline methyl ester hydrochloride in MeOH (0.5-1.0 M) was added 1.0 equiv of NaI solution in MeOH dropwise at r.t. The mixture was stirred at r.t. for an additional 1 h. After filtration to remove the NaCl, the solution was concentrated and the residue was dissolved in CH₂Cl₂ and the insoluble precipitate was filtered off again. After removal of all volatile substrates, the corresponding iodide (quantitative yield) was obtained.

23

Crystal data for 4: C₁₅H₁₆N₂O, M = 240.30, orthorhombic, space group P2₁2₁2₁, a = 7.3032 (2) Å, b = 12.2966 (6) Å, c = 13.5897 (6) Å, α = 90˚, β = 90˚, γ = 90˚, V = 1220.42 (9) Å^³, Z = 4, Dc = 1.308 Mg/m^³, m(Cu-Ka) = 0.083 mm^-¹, F(000) = 512 reflections were collected, of which 9593 were considered to be observed with I > 2σ(I). The structure was determined by direct methods using the SHELXTLTM suite of programs. Hydrogen atoms were placed in calculated positions. Full-matrix least squares refinement based on F ^² with anisotropic thermal parameters for the non-hydrogen atoms led to agreement factors R1 = 0.0360 and wR2 = 0.0887. Crystallographic data for the structure 4 reported in this paper have been deposited at the Cambridge Crystallographic Data Centre as supplementary material No. CCDC-639749. Copies of the data may be obtained, free of charge, on application to CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK (fax: [phone] or e-mail: [e-mail]).

24

Chiral stationary phase columns (Chiralcel AS for 3b and AD for 3b′).

25

Crystal data for 3b: C₂₁H₃₀N₂O₃, M = 358.47, monoclinic, space group P2₁, a = 9.4130 (4) Å, b = 19.6173 (12) Å, c = 11.8127 (7) Å, α = 90˚, β = 110.225 (3)˚, γ = 90˚, V = 2046.81 (19) Å^³, Z = 4, Dc = 1.163 Mg/m^³, m(Cu-Ka) = 0.078 mm^-¹, F(000) = 776 reflections were collected, of which 111510 were considered to be observed with I > 2σ(I). Full-matrix least squares refinement based on F ^² with anisotropic thermal parameters for the nonhydrogen atoms led to agreement factors R1 = 0.0491 and wR2 = 0.1115. Crystallographic data for the structure 3b reported in this paper have been deposited at the Cambridge Crystallographic Data Centre as supplementary material No. CCDC-639748. Copies of the data may be obtained, free of charge, on application to CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK (fax: [phone] or e-mail: [e-mail]).

29

Chiral stationary phase columns (Chiralcel AD for 9).