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Organic & Biomolecular Chemistry
Page 10 of 19
DOI: 10.1039/C7OB02545A
ARTICLE
Journal Name
1
7.21-7.12 (m, 3H), 7.10 (d,
J
= 7.5 Hz, 2H), 5.24 (dd,
= 11.8 Hz, 2H), 4.00- CDCl3) δ: 8.04 (d,
= 7.9, 5.8 Hz, 1H), 2.37 (s, 6H), 2.11- (d, = 8.2 Hz, 2H), 7.57 (d,
= 12.7, 7.2, 4.2 Hz, 4H), 1.86 (ddt, 7.41 (dd, = 8.3, 1.3 Hz, 2H), 7.35 (dd,
10.9, 7.7, 5.4 Hz, 2H); 13C NMR (126 MHz, CDCl3) δ: 138.1, (d,
= 12.5 Hz, 2H), 4.89 (d, = 12.4 Hz, 2H), 4.29 (t,
129.1, 128.6, 128.2, 125.4, 124.9, 103.1, 68.8, 66.9, 32.3, 23.4, 2H), 2.34 (td, = 11.3, 3.4 Hz, 2H), 2.23-2.15 (m, 2H), 2.12 (dt,
21.3; HRMS (ESI): calcd for C24H28NaO4: 403.1885 (M+Na)+, = 18.8, 6.6 Hz, 2H), 2.03-1.82 (m, 2H); 13C NMR (126 MHz,
J
= 4.2, 1.8 1588, 1475, 1260, 1079, 1035, 966 cm−1; H NMR (500 MHz,
Hz, 2H), 4.70 (d,
3.95 (m, 1H), 3.92 (td,
2.00 (m, 2H), 1.97 (ddd,
J
= 11.8 Hz, 2H), 4.46 (d,
J
J
= 8.4 Hz, 2H), 7.84 (d,
= 7.0 Hz, 2H), 7.48-7.43 (m, 4H),
= 8.0, 7.2 Hz, 2H), 5.10
= 6.6 Hz,
J = 8.1 Hz, 2H), 7.76
J
J
J
J
J
=
J
J
J
J
J
J
J
found: 403.1885.
CDCl3) δ: 134.0, 133.5, 131.3, 128.4, 127.9, 126.0, 125.5, 125.3,
125.2, 123.7, 107.3, 96.9, 70.5, 62.4, 28.9, 21.6; HRMS (ESI):
calcd for C30H28NaO4: 475,1885 (M+Na)+, found: 475.1872.
1,6-Bis-benzyloxy-2,7-dioxa-tricyclo[6.2.0.03,6]decane
4f.
flash chromatography (90:10 hexanes/diethyl ether), 42 %
yield (88 mg). FTIR (neat) ν: 2997, 2345, 1532, 1201, 769 cm−1; 1,6-Bis-propynoxy-2,7-dioxa-tricyclo[6.2.0.03,6]decane
4z.
1H NMR (400 MHz, CDCl3) δ: 7.27 (d,
12.2 Hz, 2H), 4.44-4.38 (m, 2H), 4.20-4.06 (m, 2H), 2.25 (td,
11.4, 3.9 Hz, 2H), 2.21-2.11 (m, 2H), 2.03 (dd,
2H), 1.94-1.84 (m, 2H); 13C NMR (101 MHz, CDCl3) δ: 136.9, CDCl3) δ: 4.17 (td,
133.0, 128.5, 128.4, 96.7, 70.2, 63.3, 28.8, 21.4; HRMS (ESI): 2.39 (t, = 2.4 Hz, 2H), 2.29-2.20 (m, 2H), 2.21-2.12 (m, 4H),
J
= 9.4 Hz, 8H), 4.58 (d,
J
J
=
=
flash chromatography (90:10 hexanes/diethyl ether), 84 %
yield (104 mg). FTIR (neat) ν: 2958, 2868, 2360, 2121, 1438,
1
J
= 20.5, 9.2 Hz, 1284, 1229, 1175, 1120, 1052, 659 cm−1; H NMR (500 MHz,
J
= 6.7, 2.9 Hz, 2H), 4.14 (d, J = 2.5 Hz, 4H),
J
calcd for C22H22Cl2NaO4: 443,0793 (M), found: 443.0810.
1.92-1.80 (m, 2H); 13C NMR (126 MHz, CDCl3) δ: 97.2, 80.3,
73.7, 70.0, 50.5, 28.9, 21.2; HRMS (ESI): calcd for C14H16NaO4:
271.0946 (M+Na)+, found: 271.0942.
1,6-Bis-benzyloxy-2,7-dioxa-tricyclo[6.2.0.03,6]decane
4h.
flash chromatography (90:10 hexanes/diethyl ether), 71% yield
(149 mg). FTIR (neat) ν: 2937, 2363, 1513, 1247, 1175, 1110, 1,6-Bis-benzylthio-2,7-dioxa-tricyclo[6.2.0.03,6]decane
1042 cm−1; 1H NMR (400 MHz, CDCl3) δ: 7.21 (t,
= 7.8 Hz, 1H), flash chromatography (90:10 hexanes/diethyl ether), 68 %
6.96-6.91 (m, 2H), 6.79 (dd, = 8.1, 2.3 Hz, 1H), 4.61 (d, = 12.1 yield (130 mg). FTIR (neat) ν: 2937, 2356, 1802, 1396, 1140,
Hz, 1H), 4.43 (d, = 7.3 Hz,
= 12.1 Hz, 1H), 4.24-4.18 (m, 1H), 3.72 (s, 1068, 771 cm−1; 1H NMR (400 MHz, CDCl3) δ: 7.38 (t,
3H), 2.27 (td, = 11.4, 3.8 Hz, 1H), 2.20-2.12 (m, 1H), 2.07 (dd, 4H), 7.31 (dd, = 13.9, 7.2 Hz, 4H), 7.24 (dd, = 13.3, 7.2 Hz,
= 21.0, 9.2 Hz, 1H), 1.90 (tdd, = 7.9 Hz, 2H), 3.91 (dd, = 17.9, 12.9 Hz, 4H),
= 11.1, 8.6, 5.6 Hz, 1H); 13C 2H), 4.10 (q,
NMR (101 MHz, CDCl3) δ: 136.4, 135.9, 129.8, 127.6, 127.3, 3.83 (t, = 11.8 Hz, 4H), 2.40-2.23 (m, 2H), 2.10-1.93 (m, 4H),
9.
J
J
J
J
J
J
J
J
J
J
J
J
J
125.7, 96.7, 70.3, 62.3, 28.8, 21.5, 18.8; HRMS (ESI): calcd for 1.93-1.72 (m, 4H); 13C NMR (101 MHz, CDCl3) δ: 138.5, 138.0,
C24H28NaO6: 435,1784 (M+Na)+, found: 435.1779.
129.2, 129.1, 128.6, 128.5, 127.1, 127.0, 76.0, 67.5, 34.9, 34.3,
29.5, 29.3; HRMS (ESI): calcd for C22H24NaO2S2: 407,1115
(M+Na)+, found: 407,1117.
1,6-Bis-benzyloxy-2,7-dioxa-tricyclo[6.2.0.03,6]decane
4k.
flash chromatography (90:10 hexanes/diethyl ether), 92 %
yield (224 mg). FTIR (neat) ν: 3002, 2984, 2307, 1612, 1515, 10. flash chromatography (90:10 hexanes/diethyl ether), 41 %
1330 cm−1; 1H NMR (400 MHz, CDCl3) δ: 7.57 (d,
7.47 (d, = 7.9 Hz, 4H), 4.68 (d, = 12.7 Hz, 2H), 4.51 (d,
12.7 Hz, 2H), 4.17 (t, = 6.5 Hz, 2H), 2.28 (td, = 11.3, 3.6 Hz, 4.52 (d,
2H), 2.22-2.12 (m, 2H), 2.05 (dd, = 19.8, 10.0 Hz, 2H), 1.91 = 14.2 Hz, 2H), 2.21-2.03 (m, 2H), 1.98-1.87 (m, 2H), 1.86-1.74
(ddd,
= 19.6, 11.0, 5.7 Hz, 2H); 13C NMR (101 MHz, CDCl3) δ: (m, 4H), 1.73-1.45 (m, 2H), 1.40-1.31 (m, 2H), 1.31-1.20 (m,
142.5, 129.5 (q, = 32.1 Hz), 127.1, 125.2, 96.8, 96.8, 70.2, 2H), 0.85 (dd,
= 10.3, 7.0 Hz, 2H).; 13C NMR (101 MHz, CDCl3)
J
= 8.1 Hz, 4H), yield (37 mg). FTIR (neat) ν: 2988, 1217, 1060 cm−1; H NMR
(400 MHz, CDCl3) δ: 7.39-7.19 (m, 10H), 4.63 (q, = 3.5 Hz, 2H),
= 12.0 Hz, 2H), 3.60 (dd, = 11.5, 4.7 Hz, 2H), 2.29 (d,
1
J
J
J
=
J
J
J
J
J
J
J
J
J
J
63.3, 28.7, 21.4; HRMS (ESI): calcd for C24H22F6NaO4: 511,1320 δ: 139.3, 130.9, 128.1, 127.2, 127.0, 96.0, 30.8, 27.8, 25.9,
(M+Na)+, found: 511.1379.
25.8, 23.9, 22.8, 22.1; HRMS (ESI): calcd for C26H32NaO4:
431,2198 (M+Na)+, found: 431,2193.
1,6-Bis-benzyloxy-2,7-dioxa-tricyclo[6.2.0.03,6]decane
4n.
flash chromatography (90:10 hexanes/diethyl ether), 90 %
yield (181 mg). Mp = 124-127° C; ATR (neat) ν: 3008, 2952, Notes and references
2914, 2881, 2857, 2231, 1611, 1507, 1418, 1380, 1330 cm−1;
1H NMR (500 MHz, CDCl3) δ: 7.63 (dd,
J
= 13.8, 8.3 Hz, 4H),
1)
(a) The Chemistry of Cyclobutanes, ed. Z. Rappoport and J. F. Liebman,
John Wiley & Sons, Chichester, 2005; (b) J. C. Namyslo and D. E.
Kaufmann, Chem. Rev. 2003, 103, 1485; (c) E. Lee-Ruff and G.
Mladenova, Chem. Rev. 2003, 103, 1449.
7.52-7.38 (m, 4H), 4.67 (d,
J
= 13.3 Hz, 2H), 4.51 (d, J = 13.3 Hz,
2H), 4.22-4.02 (m, 2H), 2.33-2.21 (m, 1H), 2.21-2.09 (m, 2H),
2.09-1.97 (m, 2H), 1.95-1.83 (m, 2H); 13C NMR (101 MHz,
CDCl3) δ: 144.1, 132.1, 127.3, 118.7, 111.7, 96.7, 70.6, 63.5,
29.4, 21.4; HRMS (ESI): calcd for C24H22N2NaO4: 425,1471
(M+Na)+, found: 425.14495.
2)
(a) F. Secci, A. Frongia, P. P. Piras, Molecules, 2013, 18, 15541; (b) M.
E. Jung, P. Davidov, Org. Lett. 2001, 3, 627; (b) H. Suginome, Y.
Nakayama, J. Chem. Soc., Perkin Trans. 1, 1992, 1843; (c) M. Zora, Y.
Li, J. W. Herndon, Organometallics, 1999, 18, 4429; (d) F. Capitta, A.
Frongia, J. Ollivier, P. P. Piras, F. Secci, Synlett, 2011, 89.
3)
(a) G. Assante, S. Dallavalle, P. A. Martino, J. Antibiotics, 2013, 66, 43;
(b) A. Arnone, C. De Gregorio, S. V. Meille, G. Nasini, G. Sidoti. J. Nat.
Prod. 1999, 62, 51.
1,6-Bis-benzyloxy-2,7-dioxa-tricyclo[6.2.0.03,6]decane
4s.
flash chromatography (90:10 hexanes/diethyl ether), 51 %
yield (115 mg). FTIR (neat) ν: 3002, 2920, 2821, 2708, 1711,
10 | J. Name., 2012, 00, 1-3
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