Synlett
DOI: 10.1055/s-0036-1590833
letter
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Star-Shaped Aromatic Derivatives with Chirality Predetermined by Bicyclo[3.3.1]nonane Framework

Gintautas Bagdžiūnas*a, Sigitas Stončiusb, Eugenijus Butkusc
  • aDepartment of Material Science and Electrical Engineering, Center for Physical Sciences and Technology, Saulėtekio av. 3, Vilnius, 10257, Lithuania   Email: gintautas.bagdziunas@ftmc.lt
  • bDepartment of Organic Chemistry, Center for Physical Sciences and Technology, Akademijos st. 7, Vilnius, 08412, Lithuania
  • cLife Sciences Center, Saulėtekio av. 7, Vilnius, 10257, Lithuania
G.B. and S.S. acknowledge support from the European Social Fund under the Global Grant measure (VP1-3.1-ŠMM-07-K-01-030).
Further Information

Publication History

Received: 17 May 2017

Accepted after revision: 15 June 2017

Publication Date:
14 July 2017 (eFirst)

Dedicated to Professor Viktoras A. Sniečkus on the occasion of his 80th anniversary

Abstract

Star-shaped aromatic derivatives of bicyclo[3.3.1]nonane with predetermined chirality were synthesized by employing the Suzuki and Sonogashira reactions. The C 3-symmetric trifunctional aromatic derivatives based on the lateral bicyclo[3.3.1]nonene moiety possess unique molecular structures. The chiroptical properties of the star-shaped compounds and the corresponding monomeric derivatives were studied, and the absolute configuration was confirmed by using the empirical octant rule for the carbonyl chromophore and the sector rule for the aromatic chromophore.

Supporting Information

 
  • References and Notes

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  • 15 Characterization Data for Representative Compounds(+)-(S, 5)-6-Oxobicyclo[3.3.1]non-2-en-2-yl Triflate (3)Colorless oil; yield: 163 mg (81%); [α]D +48.1 (c 1.04, CHCl3). 1H NMR (300 MHz, CDCl3): δ = 5.91 (dd, J = 4.8, 2.8 Hz, 1 H), 2.73 (dd, J = 6.7, 3.4 Hz, 2 H), 2.57 (ddd, J = 19.2, 7.0, 2.8 Hz, 1 H), 2.47–2.35 (m, 2 H), 2.21–1.87 (m, 5 H). 19F NMR (282 MHz, CDCl3): δ = –74.49. 13C NMR (75 MHz, CDCl3): δ = 212.1, 149.5, 118.6 (q, J = 320 Hz), 117.5, 43.0, 35.9, 32.7, 31.6, 28.4, 27.8. HRMS (EI): m/z calcd for C10H11F3O4S: 284.2521; found: 284.2532.(+)-(1S,5S)-6-Phenylbicyclo[3.3.1]non-6-en-2-one (4)Colorless crystals; yield: 36 mg (91%); mp 37–38 °C; [α]D +29.4 (c 1.09, CHCl3); IR: 2932, 1708, 1446, 761, 735, 699 cm–1; 1H NMR (300 MHz, CDCl3): δ = 7.52 – 7.21 (m, 5 H), 6.19 (dd, J = 4.5, 2.9 Hz, 1 H), 3.10–3.06 (m, 1 H), 2.76–2.78 (m, 1 H), 2.71–2.04 (m, 6 H), 2.04–1.84 (m, 2 H); 13C NMR (75 MHz, CDCl3): δ = 215.0, 141.0, 140.0, 128.8, 127.5, 125.9, 123.5, 44.2, 36.4, 32.2, 31.0, 30.9, 30.1. UV (EtOH): λmax (log ε) = 244 (4.09). CD (EtOH): λmax (Δε) = 247 (–3.0), 289 (1.5).(+)-(1S,5S)-6-(Phenylethynyl)bicyclo[3.3.1]non-6-en-2-one (5)Yellow oil; yield: 43 mg (88) [α]D +28.9 (c 1.14, CHCl3). 1H NMR (300 MHz, CDCl3): δ = 7.55–7.28 (m, 5 H), 6.31 (dd, J = 4.6, 3.0 Hz, 1 H), 2.79–2.71 (m, 1 H), 2.71–2.63 (m, 1 H), 2.62–1.85 (m, 8 H). 13C NMR (75 MHz, CDCl3): δ = 214.1, 133.2, 131.6, 128.4, 124.1, 123.4, 89.6, 88.5, 43.7, 36.0, 33.4, 30.9, 30.4. HRMS (EI): m/z calcd for C17H16O: 236.1201; found: 236.1224. UV (CH2Cl2): λmax (log ε) = 291 (3.90), 275 (3.99). CD (EtOH): λmax (Δε) = 299 (5.0), 270 (–0.50). (+)-(1S,1′S,1′′S,5S,5′S,5′′S)-6,6′,6′′-(Benzen-1,3,5-triyl)tris(bicyclo[3.3.1]non-6-en-2-one) (6)Colorless amorphous material; yield: 34 mg (70%); mp > 250 °C (dec.); [α]D +18.7 (c 1.07, CHCl3); IR: 3406, 1707, 1589, 1447, 1186, 1106, 1066 cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.36 (s, 3 H), 6.22 (dd, J = 4.3, 2.8 Hz, 3 H), 3.10 (m, 3 H), 2.80 (m, 3 H), 2.72 – 2.07 (m, 18 H), 1.98 (m, 6 H). 13C NMR (75 MHz, CDCl3): δ = 214.6, 141.4, 140.0, 124.1, 122.4, 77.6, 77.2, 76.7, 44.1, 36.2, 32.1, 31.2, 30.8, 30.0. HRMS (EI): m/z calcd for C33H36O3: 480.2664; found: 480.2668. UV (CH2Cl2): λmax (log ε) = 249 (4.41), 314 (3.42). CD (CH2Cl2): λmax (Δε) = 245 (–3.0), 308 (4.1).(+)-(1S,1′S,1′′S,5S,5′S,5′′S)-6,6′,6′′-(Benzen-1,3,5-triyltris(ethyn- 1,2-diyl))tris(bicyclo[3.3.1]non-6-en-2-one) (8)Colorless amorphous material; yield: 97 mg (86%); mp > 250 °C (dec.); [α]D +145 (c 1.23, CHCl3). IR: 2200, 1709, 1576, 1104 cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.43 (s, 3 H), 6.32 (dd, J = 4.3, 3.1 Hz, 3 H), 3.74–3.68 (m, 3 H), 2.81–2.70 (m, 3 H), 2.69–1.70 (m, 24 H). 13C NMR (75 MHz, CDCl3): δ = 213.6, 134.2, 133.8, 124.1, 123.8, 86.9, 43.6, 36.0, 33.3, 30.8, 30.3, 29.9. HRMS (EI): m/z calcd for C39H36O3: 552.2664; found: 552.2659. UV (CH2Cl2): λmax (log ε) = 297 (4.63), 281 (4.63), 268 (shoulder, 4.49). CD (CH2Cl2): λmax (Δε) = 303 (20.5), 274 (–4.4).(+)-(1S,1S,1′′S,5S,5′S,5′′S)-6,6′,6′′-(Benzen-1,3,5-triyltris(phenyl-1,4-diyl))tris(bicyclo[3.3.1]non-6-en-2-one) (10)Colorless amorphous material; yield: 20 mg (49%); mp > 250 °C (dec.); [α]D +81.8 (c 1.98, CHCl3); IR: 1708, 1512, 813 cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.80 (s, 3 H), 7.63 (dd, J = 41.7, 8.5 Hz, 12 H), 6.30 (dd, J = 4.4, 2.9 Hz, 3 H), 3.21–3.08 (m, 3 H), 2.88–2.77 (m, 3 H), 2.68 (dd, J = 18.1, 5.7 Hz, 3 H), 2.58–1.40 (m, 21 H). 13C NMR (75 MHz, CDCl3): δ = 214.8, 142.0, 140.0, 139.9, 139.3, 127.5, 126.2, 124.9, 123.7, 44.1, 36.2, 32.1, 30.8, 30.8, 30.1. HRMS (EI): m/z calcd for C51H48O3: 708.3603; found: 708.3605. UV (CH2Cl2): λmax (log ε) = 287 (4.86). CD (CH2Cl2): λmax (Δε) = 308 (18.9), 277 (–23.7).
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