Conversions of N-vinylpyridinium cations into tricyclic cage compounds

Abstract

residue which was chromatographed on a neutral alumina (activity I, CH2C12-AcOEt) column to afford the N-methyl derivative 19 (28 mg, 53%) which was identical with the sample obtained from 1 (IR and 'H NMR spectral comparison).ll-Cyan0-12-aza-l(2)-homodiamantane (22). A vigorously stirred mixture of azide 1 (225 mg, 0.98 mmol), NaCN (5 g, 102 mmol), and Adogen 464 (0.3 mL) in water (60 mL) and n-hexane (200 mL) was irradiated as above for 3.5 h. The workup and chromatography on a silica gel column (CH2C12-AcOEt) afforded the amino nitrile 22 as colorless crystals: 96 mg (43%); mp 186-188 "C; IR (KBr) 3355,2920,2230,1437,1138 cm-' ; 'H NMR (CDClJ 6 3.3-3.0 (m, l), 1.98 ( 8 , 1, D20 exchangeable), 2.5-1.3 (m, 18); mass spectrum, m / e (relative intensity) 228 (M+, loo), 227 (38).

Redox-Activated Amines in C(sp3)–C(sp) and C(sp3)–C(sp2) Bond Formation Enabled by Metal-Free Photoredox Catalysis

“…On the basis of Katritzky’s works, poor reactivity of electron-rich benzyl salts ( 36 ) can be explained by their diminished stability because of activation toward the competing nucleophilic substitution . For primary alkyl substituted substrates, the reaction proceeded remarkably slow, giving only traces of product 37 even after prolonged reaction time.…”

Orientation of Pyrylium Guests in Cucurbituril Hosts

“…Mp 182–184 °C (lit . mp 178 °C; lit . mp 181–183 °C); 1 H NMR (D 2 O) δ (ppm) 7.99 (s, 2H, H 3,5 ), 7.87 (d, 2H, J ab = 7.5 Hz, H a ), 7.49 (t (indiscernible dd), 2H, J ab = J bc = 7.5 Hz, H b ), 7.59 (t, 1H, J bc = 7.5 Hz, H c ), 3.31 (sept, 1H, J = 6.9 Hz, CH), 1.29 (d, 6H, J = 6.9 Hz, CH 3 ); HRMS calcd for C 17 H 21 O + 241.15869, found 241.02529.…”

From Amines to Alkynes – Lighting the Way

“…Based on Katritzky's works, poor reactivity of electron rich benzyl salts (29) can be explained by their diminished stability due to activation towards nucleophilic substitution. 42 For primary alkyl substituted substrates, the reaction proceeded remarkably slow, giving only traces of product 30 even after prolonged reaction time.…”

“…High selectivity of alkyl radicals towards electrophilic alkynyl tosylates compared with terminal alkynes, presented opportunity for the synthesis of unsymmetrical dialkynes via regioselective functionalization (40). Finally, silyl (42) and alkyl (43,44) substituted alkynes were also possible to obtain in workable yields, without additional optimization.…”