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Perekalin et al.
over Na, and ethyl acetate over anhydrous K2CO3. Silica gel
Merck (240—400 mesh) was used for column chromatography.
1H NMR spectra were recorded on a Bruker Avanceꢀ400 inꢀ
strument in CDCl3; chemical shifts are presented in the δ scale
relative to Me4Si. Elemental analysis was carried out at the
Laboratory of Microanalysis of the A. N. Nesmeyanov Inꢀ
stitute of Organoelement Compounds, Russian Academy of
Sciences.
Cotrimerization of diyne 2 with alkynes (general procedure).
A solution of diyne 2 (44 mg, 0.2 mmol) in CH2Cl2 (1 mL) was
added by portions to a solution of [1]BF4 (1.6 mg, 0.004 mmol),
[PhCH2NEt3]Cl (1 mg, 0.004 mmol), and alkyne (0.8 mmol) in
CH2Cl2 (1 mL) for 30 min. The mixture was stirred for 1—3 h at
room temperature. After the end of the reaction (TLC moniꢀ
toring), the reaction mixture was concentrated in vacuo. The
product was isolated by gradient column chromatography using
EtOAc—petroleum ether (from 5 : 1 to 1 : 1) as an eluent. The
fractions containing the pure product were combined, evaporatꢀ
ed, and dried in vacuo.
5´ꢀButylꢀ2,2ꢀdimethylꢀ1´,3´ꢀdihydrospiro([1,3]dioxaneꢀ5,2´ꢀ
indene)ꢀ4,6ꢀdione (3a). The yield was 52 mg (85%). 1Н NMR, δ:
0.91 (t, 3 Н, Me, J = 7.6 Hz); 1.35 (m, 2 Н, CH2); 1.56 (m, 2 Н,
CH2); 1.76 (s, 6 H, Me); 2.57 (t, 2 H, CH2, J = 7.6 Hz); 3.66
(s, 2 H, CH2); 3.67 (s, 2 H, CH2); 7.01—7.08 (m, 3 H, CH).
Found (%): C, 71.60; H, 7.38. C18H22O4. Calculated (%):
C, 71.50; H, 7.33.
5´ꢀHexylꢀ2,2ꢀdimethylꢀ1´,3´ꢀdihydrospiro([1,3]dioxaneꢀ
5,2´ꢀindene)ꢀ4,6ꢀdione (3b). The yield was 57 mg (87%). 1Н NMR,
δ: 0.87 (t, 3 Н, Me, J = 7.6 Hz); 1.29 (m, 6 Н, CH2); 1.57
(m, 2 Н, CH2); 1.81 (s, 6 H, Me); 2.57 (t, 2 H, CH2, J = 7.6 Hz);
3.68 (s, 2 H, CH2); 3.69 (s, 2 H, CH2); 7.01—7.08 (m, 3 H, CH).
Found (%): C, 72.64; H, 7.94. C20H26O4. Calculated (%):
C, 72.20; H, 7.93.
(d, 1 H, CH, J = 7.6 Hz). Found (%): C, 67.06; H, 6.71.
C17H20O5. Calculated (%): C, 67.09; H, 6.62.
2,2ꢀDimethylꢀ5´ꢀ(methoxymethyl)ꢀ1´,3´ꢀdihydrospiro([1,3]ꢀ
dioxaneꢀ5,2´ꢀindene)ꢀ4,6ꢀdione (3h). The yield was 37 mg (63%).
1Н NMR, δ: 1.81 (s, 6 Н, Me); 3.37 (s, 3 Н, Me); 3.71 (s, 4 H,
CH2); 4.43 (s, 2 H, CH2); 7.19 (m, 3 H, CH). Found (%):
C, 66.44; H, 6.19. C16H18O5. Calculated (%): C, 66.19; H, 6.25.
5´ꢀ(Acetoxymethyl)ꢀ2,2ꢀdimethylꢀ1´,3´ꢀdihydrospiro([1,3]ꢀ
dioxaneꢀ5,2´ꢀindene)ꢀ4,6ꢀdione (3i). The yield was 44 mg (69%).
1Н NMR, δ: 1.79 (s, 6 Н, Me); 2.08 (s, 3 Н, Me); 3.70 (s, 2 H,
CH2); 3.71 (s, 2 H, CH2); 5.07 (s, 2 H, CH2); 7.21 (m, 3 H, CH).
Found (%): C, 64.25; H, 5.48. C17H18O6. Calculated (%):
C, 64.14; H, 5.70.
5´ꢀ(Hexꢀ5ꢀynyl)ꢀ2,2ꢀdimethylꢀ1´,3´ꢀdihydrospiro([1,3]ꢀ
dioxaneꢀ5,2´ꢀindene)ꢀ4,6ꢀdione (3j). The yield was 52 mg (80%).
1Н NMR, δ: 1.56 (m, 4 Н, СН2); 1.71 (m, 2 Н, CH2); 1.81
(s, 6 H, Me); 1.93 (s, 1 H, CH); 2.60 (m, 2 H, CH2); 3.67 (s, 2 H,
CH2); 4.68 (s, 2 H, CH2); 7.02 (s, 1 H, CH); 7.04 (d, 1 H, CH,
J = 8.0 Hz); 7.09 (d, 1 H, CH, J = 8.0 Hz). Found (%): C, 74.16;
H, 7.00. C20H22O4. Calculated (%): C, 73.60; H, 6.79.
Compounds 4 and 5 were identified by the 1H NMR spectra
resembling the published ones.26
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 11ꢀ03ꢀ01153ꢀa)
and the Council on Grants at the President of the Russian
Federation (State Program for Support of Young Scienꢀ
tists Candidates of Science, Grant MKꢀ684.2011.3).
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2,2ꢀDimethylꢀ5´ꢀphenylꢀ1´,3´ꢀdihydrospiro([1,3]dioxaneꢀ
5,2´ꢀindene)ꢀ4,6ꢀdione (3c). The yield was 48 mg (76%). 1Н NMR,
δ: 1.83 (s, 6 Н, Me); 3.76 (s, 2 Н, CH2); 3.78 (s, 2 Н, CH2);
7.28—7.48 (m, 6 H, CH); 7.54 (d, 2 Н, СН, J = 7.2 Hz).
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2,2ꢀDimethylꢀ5´ꢀtrimethylsilylꢀ1´,3´ꢀdihydrospiro([1,3]ꢀ
dioxaneꢀ5,2´ꢀindene)ꢀ4,6ꢀdione (3d). The yield was 34 mg (54%).
1Н NMR, δ: 0.24 (s, 9 Н, Me); 1.82 (s, 6 Н, Me); 3.72 (s, 2 H,
CH2); 3.73 (s, 2 H, CH2); 7.20 (d, 1 H, CH, J = 7.6 Hz); 7.37
(m, 2 H, CH). Found (%): C, 64.49; H, 6.85. C17H22O4Si. Calꢀ
culated (%): C, 64.12; H, 6.96.
5´,6´ꢀDiethylꢀ2,2ꢀdimethylꢀ1´,3´ꢀdihydrospiro([1,3]dioxaneꢀ
5,2´ꢀindene)ꢀ4,6ꢀdione (3e) was synthesized similarly using
10 equiv. of hexꢀ3ꢀyne. The yield was 39 mg (65%). 1Н NMR, δ:
1.19 (t, 6 Н, Me, J = 7.6 Hz); 1.81 (s, 6 Н, Me); 2.62 (q, 4 H,
CH2, J = 7.6 Hz); 3.67 (s, 4 H, CH2); 7.00 (s, 2 H, CH).
Found (%): C, 71.13; H, 7.31. C18H22O4. Calculated (%):
C, 71.50; H, 7.33.
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2,2ꢀDimethylꢀ1´,3´ꢀdihydrospiro([1,3]dioxaneꢀ5,2´ꢀindene)ꢀ
4,6ꢀdione (3f). The yield was 27 mg (54%). Н NMR, δ: 1.82
14. E. E. Karslyan, A. I. Konovalov, D. S. Perekalin, P. V. Petroꢀ
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1
(s, 6 Н, Me); 3.73 (s, 4 H, CH2); 7.22 (m, 4 H, CH). Found (%):
C, 68.26; H, 5.77. C14H14O4. Calculated (%): C, 68.28; H, 5.73.
5´ꢀ(3ꢀHydroxypropyl)ꢀ2,2ꢀdimethylꢀ1´,3´ꢀdihydrospiro([1,3]ꢀ
dioxaneꢀ5,2´ꢀindene)ꢀ4,6ꢀdione (3g). The yield was 46 mg (75%).
1Н NMR, δ: 1.81 (s, 6 Н, Me); 1.85 (m, 2 H, CH2); 2.16 (s, 1 H,
OH); 2.68 (t, 2 H, CH2, J = 8.0); 3.68 (m, 2 H, CH2); 3.69 (s, 4 H,
CH2); 7.04 (s, 1 H, CH); 7.07 (d, 1 H, CH, J = 7.6 Hz); 7.10