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Synlett 2008(2): 203-206  
DOI: 10.1055/s-2007-1000873
LETTER
© Georg Thieme Verlag Stuttgart · New York

Hydrogen-Bonded Arrays Coupled by Cross-Metathesis

Eric J. Enholm*, Jed M. Hastings, Chris Edwards
Department of Chemistry, University of Florida, Gainesville, FL 32611, USA
Fax: +1(352)3928758; e-Mail: enholm@chem.ufl.edu;
Further Information

Publication History

Received 24 April 2007
Publication Date:
21 December 2007 (online)

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Abstract

Recently, supramolecular assemblies have been created as responsive, reversible, and dynamic materials. By a modular approach, we discuss the reversible cross-metathesis of terminal olefins containing self-complementary hydrogen-bond donor and acceptor arrays. These compounds are readily constructed from 2,6-diaminotriazines or cytosine and chiral elements can be installed from modified amino acids. Dynamic combinatorial libraries should be accessible via this approach.

Key words

metathesis - amino acids - ruthenium - supramolecular chemistry - dimerizations

9

The NMR methods to obtain the Kdim values for 5 and 8 will be published in an upcoming paper.

10

Analytical Data
Compound 3:11 1H NMR (300 MHz, DMSO-d 6): δ = 10.22 (s, 1 H), 8.31 (d, 2 H, J = 8.01 Hz), 7.55 (m, 5 H), 3.34 (s, 3 H) ppm. 13C NMR (75 MHz, DMSO-d 6): δ = 171.8, 171.2, 168.4, 164.9, 137.0, 132.8, 129.3, 128.8, 26.4 ppm.
Compound 4: mp 188-191 °C. 1H NMR (300 MHz, DMSO-d 6): δ = 8.35 (d, 2 H, J = 7.74 Hz), 7.94 (s, 1 H), 7.48 (m, 5 H), 1.33 (s, 9 H) ppm. 13C NMR (75 MHz, DMSO-d 6): δ = 176.5, 173.1, 168.3, 164.5, 136.1, 132.6, 128.9, 40.9, 27.8 ppm.
Compound 5: 1H NMR (300 MHz, DMSO-d 6): δ = 8.63 (s, 1 H), 8.58 (s, 1 H), 8.46 (d, 2 H, J = 6.18 Hz), 7.53 (m, 3 H), 5.96 (m, 1 H), 5.11 (m, 2 H), 3.19 (t, 2 H, J = 7.28 Hz), 2.55 (q, 2 H, J = 7.16 Hz), 1.38 (s, 9 H) ppm. 13C NMR (75 MHz, DMSO-d 6): δ = 176.1, 173.9, 173.5, 164.5, 164.0, 136.8, 134.8, 133.1, 129.0, 128.6, 115.5, 40.7, 37.1, 28.5, 27.2 ppm.
Compound 7: mp 183-188 °C. 1H NMR (300 MHz, DMSO-d 6): δ = 7.51 (d, 1 H, J = 7.03 Hz), 7.00 (s, 2 H), 5.76 (m, 1 H), 5.61 (d, 1 H, J = 7.33 Hz), 4.94 (m, 2 H), 3.57 (t, 2 H, J = 7.04 Hz), 1.93 (q, 2 H, J = 7.04 Hz), 1.59 (pent, 2 H, J = 7.03 Hz) ppm. 13C NMR (75 MHz, DMSO-d 6): δ = 166.5, 156.4, 146.6, 138.3, 115.7, 93.7, 48.8, 40.9, 30.7, 28.3 ppm.
Compound 8: 1H NMR (300 MHz, DMSO-d 6): δ = 10.92 (s, 1 H), 8.99 (s, 1 H), 7.56 (s, 1 H), 7.42 (d, 1 H, J = 7.18 Hz), 5.79 (m, 1 H), 5.05, (m, 2 H), 3.83 (t, 2 H, J = 7.18 Hz), 3.25 (q, 2 H, J = 5.64 Hz), 2.12 (q, 2 H, J = 7.18 Hz), 1.86 (pent, 2 H, J = 7.44 Hz), 1.56 (pent, 2 H, J = 7.18 Hz), 1.38 (sext, 2 H, J = 7.95 Hz), 0.92 (t, 3 H, J = 7.43 Hz) ppm. 13C NMR (75 MHz, DMSO-d 6): δ = 154.3, 149.9, 146.7, 136.8, 115.9, 97.3, 50.2, 39.7, 31.5, 30.4, 27.7, 20.1, 13.8 ppm. HRMS (LSIMS+): m/z calcd: 278.1743; found: 279.1812 [M + H].
Compound 9: 1H NMR (300 MHz, DMSO-d 6): δ = 11.03 (s, 1 H), 9.72 (s, 1 H), 7.41 (s, 1 H), 7.40 (d, 1 H, J = 7.30 Hz), 7.26 (m, 5 H), 5.74 (m, 1 H), 4.96 (m, 2 H), 4.59 (q, 1 H, J = 6.43 Hz), 4.09 (t, 2 H, J = 6.57 Hz), 3.15 (m, 2 H), 2.02 (q, 2 H, J = 7.89, 6.43 Hz), 1.67 (m, 5 H), 1.31 (m, 5 H), 0.88 (t, 3 H, J = 6.72 Hz) ppm. 13C NMR (75 MHz, DMSO-d 6): δ = 172.2, 164.7, 154.3, 146.7, 137.5, 129.2, 128.3, 126.6, 115.1, 97.3, 64.4, 55.3, 50.8, 37.3, 29.9, 27.7, 22.3, 13.9 ppm.
Compound 11: [α]20 -59.0; mp 110-112 °C. 1H NMR (300 MHz, DMSO-d 6): δ = 11.03 (s, 2 H), 9.62 (s, 2 H), 7.26 (m, 12 H), 5.23 (s, 2 H), 4.51 (s, 2 H), 3.99 (s, 4 H), 3.74 (s, 4 H), 3.06 (m, 4 H), 1.86 (s, 4 H), 1.65 (m, 10 H), 1.23 (s, 10 H), 0.81 (s, 6 H) ppm. 13C NMR (75 MHz, DMSO-d 6): δ = 172.0, 164.5, 157.0, 154.3, 146.9, 137.5, 129.8, 129.2, 128.2, 126.5, 97.3, 64.2, 55.5, 50.7, 37.2, 28.5, 22.2, 13.8, 0.96 ppm. HRMS: m/z calcd: 440.2424; found: 441.2502 [M + H].
Compound 12: mp 236-240 °C. 1H NMR (300 MHz, DMSO-d 6): δ = 10.70 (s, 2 H), 10.19 (s, 2 H), 8.41 (d, 4 H, J = 7.16 Hz), 7.54 (m, 6 H), 5.57 (s, 2 H), 2.84 (m, 4 H), 2.30 (s, 4 H), 1.25 (s, 18 H) ppm. 13C NMR (75 MHz, DMSO-d 6): δ = 176.1, 172.5, 172.0, 135.2, 132.6, 129.3, 128.6, 128.4, 36.8, 27.3, 26.5 ppm.
Compound 13: 1H NMR (300 MHz, DMSO-d 6): δ = 9.67 (s, 2 H), 8.87 (s, 2 H), 7.80 (d, 2 H, J = 6.9 Hz), 6.09 (s, 2 H), 5.34 (s, 2 H), 3.63 (s, 4 H), 3.08 (d, 4 H, J = 5.7 Hz), 1.91 (m, 4 H), 1.26 (m, 12 H), 0.80 (t, 6 H, J = 6.9 Hz) ppm. 13C NMR (75 MHz, DMSO-d 6): δ = 162.4, 153.7, 148.5, 137.6, 115.3, 94.1, 49.0, 42.2, 31.5, 30.0, 27.3, 19.5, 13.6 ppm. HRMS: m/z calcd 679.3469 [M + H]; found: 679.3397 [M + H].
Compound 14: mp 184-187 °C. 1H NMR (300 MHz, DMSO-d 6): δ = 11.03 (s, 2 H), 9.62 (s, 2 H), 7.26 (m, 12 H), 5.23 (s, 2 H), 4.51 (s, 2 H), 3.99 (s, 4 H), 3.74 (s, 4 H), 3.06 (m, 4 H), 1.86 (s, 4 H), 1.65 (m, 10 H), 1.23 (s, 10 H), 0.81 (s, 6 H) ppm. 13C NMR (75 MHz, DMSO-d 6): δ = 172.0, 164.5, 157.0, 154.3, 146.9, 137.5, 129.8, 129.2, 128.2, 126.5, 97.3, 64.2, 55.5, 50.7, 37.2, 28.5, 22.2, 13.8, 0.96 ppm. HRMS: m/z calcd 529.3245 [M + H]; found: 529.3257 [M + H].
Compound 15: mp 230-235 °C. 1H NMR (300 MHz, CDCl3): δ = 10.89 (br s, 1 H), 9.04 (s, 1 H), 8.81 (s, 2 H), 8.43 (d, 2 H, J = 7.31 Hz), 5.53 (m 3 H), 3.80 (m, 2 H), 3.09 (t, 2 H, J = 7.01 Hz), 2.48 (q, 2 H, J = 7.16 Hz), 2.05 (m, 2 H), 1.81 (p, 2 H, J = 7.02), 1.52 (m, 1 H), 1.36 (s, 9 H), 1.26-1.16 (m, 5 H), 0.90 (t, 3 H, J = 7.46) ppm. 13C NMR (75 MHz, CDCl3): δ = 176.6, 174.2, 173.7, 164.8, 154.1, 147.1, 135.1, 133.3, 130.1, 130.0, 129.2, 128.8, 66.1, 54.2, 50.4, 47.8, 40.9, 37.9, 29.6, 28.4, 27.8, 27.4, 24.5, 20.5, 15.5, 10.9 ppm.