3,4-Methano-β-Proline: A Conformationally Constrained β-Amino Acid

Abstract

An enantiomerically pure, conformationally constrained β-proline derivative, 3,4-methano-β-proline, was synthesized starting with a readily available bicyclic lactone by using a straightforward synthetic route.

3,4-methano-β-proline - conformationally constrained β-amino acid - enantioselective synthesis

References and Notes

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<A NAME="RU12308ST-18">18</A>

HPLC Data for Boc-(3 R ,4 R )-Methano-β-proline Methyl Ester
t _R = 13.622 (min), area = 100%; OJ-H, IPA-n-hexane = 5:95; flow rate = 0.4 mL/min, 25 ˚C, λ = 220 nm.

<A NAME="RU12308ST-19">19</A>

Crystal Data for Compound 1
C₁₁H₁₇NO₄, crystal size: 0.10 × 0.20 × 0.20 mm^³, M _r = 227.26 g mol^-¹, monoclinic, space group P21, λ = 0.71073 Å, a = 6.1437 (8) Å, b = 11.3449 (17) Å, c = 9.3146 (13) Å, α = 90, β = 104.369 (10), γ  = 90, V = 628. 92 (15) Å^³, Z = 2, ρ _calcd = 1.200 g cm^-³, µ  = 0.091 min^-¹, T = 293 (2) K, θ range = 3.6-33.2˚; reflections collected: 10063, independent: 4247 (R _int = 0.037). The structure was solved by direct methods and refined by full-matrix least-squares on F^²; R ₁ = 0.0432, wR ₂ = 0.1196 [ I > 2σ (I)]; maximal residual electron density: 0.12 e Å^-³. CCDC 710057 contains the supplementary crystallographic data for this structure. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

<A NAME="RU12308ST-20">20</A> Flack HD. Acta Crystallogr., Sect. A: Fundam. Crystallogr.  1983,  39:  876 ; the Flack parameter of the crystal structure of 1 was 0.0(10), and that of ent-1 was 1.0(10)

<A NAME="RU12308ST-21">21</A>

HPLC Data for Boc-(3 R )-β-proline Methyl Ester
t _R = 20.621 (min), area = 100%; racemic Boc-β-proline methyl ester, t _R = 15.985, 20.824 (min). OJ-H, IPA-n-hexane = 5:95; flow rate = 0.4 mL/min, 25 ˚C, λ = 220 nm.