Synlett 2020; 31(07): 672-676
DOI: 10.1055/s-0039-1691586
letter
© Georg Thieme Verlag Stuttgart · New York

Unusual Transformations of Cyclic Allenes with an Enamine Moiety into Complex Frameworks

a  Organic Chemistry Department, Peoples’ Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya St, Moscow 117198, Russian Federation   Email: titov-aa@rudn.ru
,
Maxim S. Kobzev
a  Organic Chemistry Department, Peoples’ Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya St, Moscow 117198, Russian Federation   Email: titov-aa@rudn.ru
,
Tatiana N. Borisova
a  Organic Chemistry Department, Peoples’ Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya St, Moscow 117198, Russian Federation   Email: titov-aa@rudn.ru
,
Elena A. Sorokina
a  Organic Chemistry Department, Peoples’ Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya St, Moscow 117198, Russian Federation   Email: titov-aa@rudn.ru
,
Erik Van der Eycken
a  Organic Chemistry Department, Peoples’ Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya St, Moscow 117198, Russian Federation   Email: titov-aa@rudn.ru
b  Laboratory for Organic and Microwave-Assisted Chemistry (LOMAC), Department of Chemistry, University of Leuven (KU Leuven), Celestijnenlaan 200F, Leuven 3001, Belgium
,
Alexey V. Varlamov
a  Organic Chemistry Department, Peoples’ Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya St, Moscow 117198, Russian Federation   Email: titov-aa@rudn.ru
,
Leonid G. Voskressensky
a  Organic Chemistry Department, Peoples’ Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya St, Moscow 117198, Russian Federation   Email: titov-aa@rudn.ru
› Author Affiliations
The publication has been prepared with the support of the ‘RUDN University Program 5-100’ and by the Russian Foundation for Basic Research (projects No. 18-33-00526, 17-03-00605).
Further Information

Publication History

Received: 05 December 2019

Accepted after revision: 08 January 2020

Publication Date:
04 February 2020 (online)


Abstract

The thermolysis reactions of benzoazacyclodecatrienes under microwave irradiation conditions in toluene at 150 °C afforded complex azabenzo[a]cyclopropa[cd]azulene and (epiminomethano)cyclopenta[a]indene frameworks. Cyclopropanes were established as intermediates of the ultimate thermolysis products.

Supporting Information

Primary Data

 
  • References and Notes

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  • 13 Methyl 8-Isopropyl-10,11-dimethoxy-3-methyl-6-phenyl-3-azabenzo[d]cyclodeca-4,6,7-triene-5-carboxylate (4b) Colorless crystals; yield: 438 mg (92%); mp 175–176 °C; Rf  = 0.44 (EtOAc–hexane, 1:2). IR (KBr): 1956, 1055 (C=C=C), 1684 (С=O) cm–1. 1H NMR (600 MHz, CDCl3): δ = 7.61 (s, 1 H), 7.33–7.30 (m, 2 H), 7.25–7.23 (m, 2 H), 7.14–7.12 (m, 1 H), 6.88 (s, 1 H), 6.59 (s, 1 H), 4.18–4.14 (m, 1 H), 3.91 (s, 3 H), 3.85 (s, 3 H), 3.61 (s, 3 H), 3.50–3.46 (m, 1 H), 3.16 (s, 3 H), 2.94 (sept, J = 6.7, 1 H), 2.81–2.70 (m, 2 H), 1.35 (d, J = 6.7 Hz, 3 H), 1.02 (d, J = 6.7 Hz, 3 H). 13C NMR (150 MHz, CDCl3): δ = 206.0, 170.7, 147.9, 147.6, 147.4, 138.3, 129.3, 128.7, 128.2 (2 C), 126.3, 125.7 (2 C), 112.9, 111.5, 110.5, 103.5, 96.0, 56.1, 55.9, 51.8, 51.1, 45.1, 31.7, 31.0, 22.2, 21.2. LC-MS (ESI): m/z = 434 [M + H]+. Anal. Calcd for C27H31NO4: C, 74.80; H, 7.21; N, 3.23. Found: C, 74.95; H, 7.41; N, 3.37.
  • 14 Methyl 10,11-Dimethoxy-3-methyl-6,8-diphenyl-3-azabenzo[d]cyclodeca-4,6,7-triene-5-carboxylate (4d) Colorless crystals; yield: 473 mg (92%); mp 210–212 °C. Rf  = 0.47 (EtOAc–hexane, 1:1). IR (KBr): 1947, 1059 (C=C=C), 1690 (С=O) cm–1. 1H NMR (600 MHz, DMSO-d 6): δ = 7.58 (s, 1 H), 7.42–7.38 (m, 4 H), 7.34–7.29 (m, 5 H), 7.22–7.20 (m, 1 H), 6.93 (s, 1 H), 6.70 (s, 1 H), 3.89–3.85 (m, 1 H), 3.76 (s, 3 H), 3.61 (s, 3 H), 3.47 (s, 3 H), 3.29–3.25 (m, 1 H), 3.17 (s, 3 H), 3.07–3.02 (m, 1 H), 2.98–2.92 (m, 1 H). 13C NMR (150 MHz, DMSO-d 6): δ = 209.1, 168.4, 148.1, 147.7, 147.2, 137.4, 136.5, 129.5, 128.8 (2 C), 128.7 (2 C), 127.4, 127.3 (2 C), 127.1, 125.9, 125.5 (2 C), 113.7, 112.8, 107.0, 104.7, 93.1, 55.6, 55.5, 50.9, 50.7, 44.6, 30.2. LC-MS (ESI): m/z = 468 [M + H]+. Anal. Calcd for C30H29NO4: C, 77.06; H, 6.25; N, 3.00. Found: C, 77.19; H, 6.33; N, 3.13.
  • 15 General Procedure A A solution of the appropriate allene derivative (0.68 mmol) in dry toluene (6.0 mL) was placed in a microwave reactor and heated at 150 °C for 30 min while the progress of the reaction was monitored by TLC [EtOAc–hexane, 1:1 (4a and 4c); EtOAc–hexane, 1:2 (4b, 4d, and 4e)]. The solvent was evaporated in vacuo. Products 7ac, 7e, and 8ae were isolated by chromatography on silica gel; compounds 7a and 7c, 7b and 8b, 7e, 8a, 8c, and 8e were eluted with EtOAc–hexane (1:3, 1:5, 1:12, 1:2, 1:1, and 1:10, respectively).
  • 16 General Procedure B A solution of the appropriate allene derivative (0.16 mmol) in dry toluene (6.0 mL) was irradiated in a microwave reactor at 150 °C for 3–7.5 h with stirring while the progress of the reaction was monitored by TLC [EtOAc–hexane, 1:1 (4a and 4c); EtOAc–hexane, 1:2, (4b, 4d, and 4e)]. The solvent was evaporated in vacuo and products 8ae were crystallized from Et2O.
  • 17 Methyl 6,7-Dimethoxy-2,4b-dimethyl-4a-phenyl-1,2,4a,4b,8b,8c-hexahydro-2-azabenzo[a]cyclopropa[cd]azulene-4-carboxylate (7a) Colorless crystals; yield: 162 mg (59%) (Procedure A); mp 153–155 °C. Rf  = 0.47 (EtOAc–hexane, 1:1). IR (KBr): 1682 (C=O) cm–1. 1H NMR (600 MHz, CDCl3): δ = 7.57–7.56 (m, 2 H), 7.26–7.24 (m, 2 H), 7.15–7.13 (m, 1 H), 6.87 (s, 1 H), 6.74 (s, 1 H), 6.50 (s, 1 H), 4.22 (dd, J = 14.1, 1.5 Hz, 1 H), 3.88 (s, 3 H), 3.85 (s, 3 H), 3.77–3.75 (m, 1 H), 3.58 (dd, J = 14.1, 5.6 Hz, 1 H), 3.44 (s, 3 H), 3.00 (s, 3 H), 2.12 (d, J = 6.6 Hz, 1 H), 1.71 (s, 3 H). 13C NMR (150 MHz, CDCl3): δ = 168.7, 147.5, 147.4, 146.7, 144.1, 140.1, 134.6, 131.1 (2 C), 127.3 (2 C), 125.3, 107.5, 106.8, 98.0, 55.8, 55.6, 51.4, 49.8, 46.5, 42.1, 39.1, 37.8, 37.0, 16.2. LC-MS (ESI): m/z = 406 [M + H]+. Anal. Calcd for C25H27NO4: C, 74.05; H, 6.71; N 3.45. Found: C, 74.21; H, 6.86; N, 3.55. Methyl 5,6-Dimethoxy-2,11-dimethyl-14-phenyl-11-azatetracyclo[7.5.0.02,12.03,8]tetradeca-3,5,7,13-tetraene-13-carboxylate (8a) Colorless crystals; yield: 32 mg (50%) (Procedure B); 3 mg (1%) (Procedure A); mp 149–151 °C. Rf  = 0.52 (EtOAc–hexane, 1:1). IR (KBr): 1694 (C=O) cm–1. 1H NMR (600 MHz, CDCl3): δ = 7.49–7.47 (m, 2 H), 7.41–7.35 (m, 3 H), 6.74 (s, 1 H), 6.73 (s, 1 H), 3.92 (s, 3 H), 3.89 (s, 3 H), 3.70 (s, 3 H), 3.68 (d, J = 1.7 Hz, 1 H), 3.23 (d, J = 4.1 Hz, 1 H), 3.12–3.11 (m, 1 H), 2.66 (dd, J = 10.7, 2.5 Hz, 1 H), 2.48 (dd, J = 10.7, 2.5 Hz, 1 H), 2.22 (s, 3 H), 1.48 (s, 3 H). 13C NMR (150 MHz, CDCl3): δ = 166.3, 151.1, 148.3, 147.8, 137.3, 137.1, 135.1, 128.5, 128.0 (2 C), 127.9 (2 C), 124.9, 107.1, 106.9, 72.8, 67.9, 59.6, 55.8, 55.7, 51.2, 51.1, 42.6, 42.3, 18.3. LC-MS (ESI): m/z = 406 [M + H]+. Anal. Calcd for C25H27NO4: C, 74.05; H, 6.71; N, 3.45. Found: C, 74.28; H, 6.91; N, 3.56.
  • 18 CCDC 1830405 and CCDC 1579823 contain the supplementary crystallographic data for compounds 7a and 8a, respectively. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
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  • 23 General Procedure C A solution of compound 7a (0.24 mmol) in absolute toluene (6.0 mL) was irradiated in a microwave reactor at 150 °C for 2 h with stirring while the progress of the reaction was monitored by TLC (EtOAc–hexane, 1:1). The solvent was then evaporated in vacuo and product 8a was crystallized from Et2O; yield: 49 mg (50%).
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