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Synlett 2018; 29(06): 793-798
DOI: 10.1055/s-0037-1609094
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© Georg Thieme Verlag Stuttgart · New York

Synthesis of Optically Pure (S,E)-2-Amino-5-arylpent-4-enoic Acids by Heck Reactions of Nickel Complexes

Silvio Parpart
a   Universität Rostock, Institut für Chemie, A.-Einstein-Str. 3a, 18059 Rostock, Germany   Email: peter.langer@uni-rostock.de
,
Zorayr Z. Mardiyan
a   Universität Rostock, Institut für Chemie, A.-Einstein-Str. 3a, 18059 Rostock, Germany   Email: peter.langer@uni-rostock.de
c   SPC ‘Armbiotechnology’ SNPO NAS RA, Gyurjyan Str. 14, 0056 Yerevan, Armenia
d   Yerevan State University, Faculty of Pharmacy and Chemistry, Chair of Pharmacy, Alex Manoogyan Str. 1, 0025 Yerevan, Armenia
,
Peter Ehlers
a   Universität Rostock, Institut für Chemie, A.-Einstein-Str. 3a, 18059 Rostock, Germany   Email: peter.langer@uni-rostock.de
b   Leibniz-Institut für Katalyse e.V. an der Universität Rostock, A.-Einstein-Str. 29a, 18059 Rostock, Germany
,
Andranik Petrosyan
a   Universität Rostock, Institut für Chemie, A.-Einstein-Str. 3a, 18059 Rostock, Germany   Email: peter.langer@uni-rostock.de
b   Leibniz-Institut für Katalyse e.V. an der Universität Rostock, A.-Einstein-Str. 29a, 18059 Rostock, Germany
d   Yerevan State University, Faculty of Pharmacy and Chemistry, Chair of Pharmacy, Alex Manoogyan Str. 1, 0025 Yerevan, Armenia
,
Anna F. Mkrtchyan
c   SPC ‘Armbiotechnology’ SNPO NAS RA, Gyurjyan Str. 14, 0056 Yerevan, Armenia
d   Yerevan State University, Faculty of Pharmacy and Chemistry, Chair of Pharmacy, Alex Manoogyan Str. 1, 0025 Yerevan, Armenia
,
Ashot S. Saghyan
c   SPC ‘Armbiotechnology’ SNPO NAS RA, Gyurjyan Str. 14, 0056 Yerevan, Armenia
d   Yerevan State University, Faculty of Pharmacy and Chemistry, Chair of Pharmacy, Alex Manoogyan Str. 1, 0025 Yerevan, Armenia
,
Peter Langer  *
a   Universität Rostock, Institut für Chemie, A.-Einstein-Str. 3a, 18059 Rostock, Germany   Email: peter.langer@uni-rostock.de
b   Leibniz-Institut für Katalyse e.V. an der Universität Rostock, A.-Einstein-Str. 29a, 18059 Rostock, Germany
› Author AffiliationsFinancial support by the State of Mecklenburg-Vorpommern, by the DAAD (Ostpartnerschaften program), and by the Volkswagenstiftung is gratefully acknowledged.
Further Information

Publication History

Received: 25 October 2017

Accepted after revision: 26 November 2017

Publication Date:
15 January 2018 (online)

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Abstract

Starting from commercially available building blocks a variety of enantiomerically pure (S)-2-amino-4-enoic acids has been synthesized by the Heck reaction using Ni-(S)-BPB {Nickel-N-[(S)-benzylprolyl]aminobenzophenone} as a chiral auxiliary. The reactions proceeded in very good yields and with high E-selectivity.

Key words

amino acids - Heck reaction - catalysis - chiral auxiliary - ­enantioselectivity

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1609094.
  • Supporting Information
 

  • References and Notes

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  • 21 (S,E)-2-Amino-2-methyl-5-[phenyl]pent-4-enoic acid–Ni–(S)-BPB (3a) Compound 2b (221 mg, 1.0 equiv), Pd(PPh3)4(23 mg, 0.05 equiv), and bromobenzene (72 μl, 1.7 equiv) were added to a pressure tube and dissolved in 1,4-dioxane (6 ml, 15 l/mol 2b) and HN i Pr2 (6 mL, 15 l/mol 2b). The mixture was stirred at 101 °C for 24 h. After cooling to room temperature it was diluted with ethyl acetate and washed with water. The organic layer was dried with Na2SO4 and filtered. The solvent was removed under reduced pressure, and the residue was purified by silica column chromatography (ethyl acetate/heptanes, 2:1 >> 1:0) to yield 3a as a red solid; yield 88%, mp 112–113 °C. 1H NMR (250 MHz, CDCl3): δ = 1.27 (s, 3 H, CH3), 1.35–1.74 (m, 1 H, CH2), 1.82–1.99 (m, 1 H, CH2), 2.01–2.25 (m, 2 H, CH2), 2.48–2.73 (m, 3 H, CH2), 3.27 (dd, 3 J = 9.8 Hz, 3 J = 7.1, 1 H, CH), 3.42–3.55 (m, 1 H, CH2), 3.61 (d, 2 J = 12.7 Hz, 1 H, CH2Ph), 4.40 (d, 2 J = 12.7 Hz, 1 H, CH2Ph), 6.58–6.74 (m, 3 H, CH), 6.85–7.00 (m, 1 H, CH), 7.03–7.19 (m, 2 H, CH), 7.21–7.57 (m, 11 H, CH), 7.61–7.74 (m, 1 H, CH), 7.96–8.10 (m, 3 H, CH). 13C NMR (63 MHz, CDCl3): δ = 23.1 (CH3), 29.7, 30.7, 43.9, 63.6 (CH2), 70.2 (CH), 78.7 (C), 120.9, 124.0, 124.2, 126.8, 127.2, 127.7, 128.0, 128.3 (CH), 128.7 (C) 128.8, 129.0, 129.1, 129.7, 130.8, 131.9 (CH), 133.5 (C), 133.7, 134.7 (CH), 136.8, 137.3, 142.0 (C), 172.8 (C=N), 180.7 (C=O), 181.9 (C=O). IR (ATR): ν = 3057 (w), 3025 (w), 2922 (br, w), 2867 (w), 1668 (m), 1634 (s), 1594 (w), 1574 (w), 1534 (w), 1495 (w), 1469 (w), 1436 (m), 1355 (s), 1331 (m), 1312 (w), 1287 (w), 1250 (s), 1163 (m), 1118 (w), 1062 (w), 1000 (w), 964 (m), 927 (w), 885 (w), 824 (w), 748 (s), 695 (s), 618 (w), 563 (w), 540 (m) cm–1. MS (EI, 70 eV): m/z (%) = 627 (5) [M+], 585 (15), 584 (13), 583 (32), 510, (7), 492 (4), 440 (4), 439 (4), 425 (4), 347 (1), 328 (2), 280 (2), 278 (2), 161 (9), 160 (89). ESI-HRMS: m/z calcd for C37H36N3NiO3 [M + H+]: 628.21047; found: 628.20997; m/z calcd for C37H36N3 60NiO3 [M + H+]: 630.20798; found: 630.20805; m/z calcd for C37H35N3NiNaO3 [M + Na+]: 650.19241; found: 650.19232; m/z calcd for C37H35N3Na60NiO3 [M + Na+]: 652.18992; found: 652.18952.
  • 22 (S,E)-2-Amino-2-methyl-5-[phenyl]pent-4-enoic acid (4a) Compound 3a (190 mg, 1.0 equiv) was dissolved in MeOH/H2O (10 ml/5 ml), and HCl (12 M, 1.5 ml) was added dropwise. The stirred mixture was heated to reflux for 20 min (during which time the color changed from red to green). After cooling to room temperature the mixture was diluted with water and extracted with DCM four times. The aqueous layer was treated with 5% aq NH3solution to reach pH 2. The solution was further purified by cation exchange column (Dowex 50WX8 H+, see Supporting Information for details) to yield 4a as white solid; yield 85%, mp 267–268 °C. 1H NMR (300 MHz, CD3OD): δ = 1.64 (s, 3 H, CH3), 2.79 (dd, 3 J = 7.6 Hz, 2 J = 14.5 Hz, 1 H, CH2), 2.87 (dd, 3 J = 7.6 Hz, 2 J = 14.5 Hz, 1 H, CH2), 6.21 (dt, 3 J = 7.6 Hz, 3 J = 15.4 Hz, 1 H, C=C), 6.65 (d, 3 J = 15.4 Hz, 1 H, C=C), 7.19–7.34 (m, 3 H, Ph), 7.40–7.45 (m, 2 H, Ph). 13C NMR (75 MHz, CD3OD): δ = 22.7 (CH3), 41.8 (CH2), 61.2 (C), 121.8 (CH), 127.7, 129.1, 129.7, 137.8 (CH), 138.1 (C), 173.5 (COOH). IR (ATR): ν = 3000 (br, m), 1656 (br, w), 1540 (w), 1573 (s), 1494 (w), 1450 (w), 1397 (s), 1366 (m), 1287 (w), 1264 (w), 1239 (w), 1130 (w), 1070 (w), 965 (s), 883 (w), 788 (w), 739 (s), 690 (s), 629 (w), 587 (w), 553 (w) cm–1. MS (EI, 70 eV): m/z (%) = 206 (4), 205 (2) [M+], 194 (5), 193 (13), 178 (4), 161 (6), 160 (64), 159 (12), 144 (12), 143 (16), 129 (13), 128 (34), 118 (31), 117 (87), 116 (50), 115 (86), 102 (12), 91 (60), 90 (6), 89 (42), 88 (100), 80 (16), 77 (15), 65 (13), 63 (11). HRMS (EI): m/z calcd for C12H16NO2 [M + H+]: 206.11756; found: 206.11778.