Categories: Synthesis of O-Heterocyles >
Related: benzo-fused S-Heterocyles, benzo-fused N-Heterocycles

Synthesis of benzo-fused O-Heterocycles and similar compounds

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Recent Literature

A nucleophilic substitution of alkyl fluorides was achieved in intramolecular reactions with O- and N-nucleophiles. The reaction is influenced by the nature of nucleophiles, the size of the ring to be formed, and the comformational rigidity of the precursors.
L. Zhang, W. Zhang, J. Liu, J. Hu, J. Org. Chem., 2009, 74, 2850-2853.

A broad range of substituted benzisoxazolines have been synthesized by a mild [3 + 2] cycloaddition of nitrones and arynes. The process tolerates various functional groups.
C. Lu, A. V. Dubrovskiy, R. C. Larock, J. Org. Chem., 2012, 77, 2279-2284.

Sequential coupling-imination-annulation reactions of ortho-bromoarylaldehydes and terminal alkynes with ammonium acetate in the presence of a palladium catalyst under microwave irradiation gives various substituted isoquinolines, furopyridines, and thienopyridines in good yields.
D. Yang, S. Burugupalli, D. Daniel, Y. Chen, J. Org. Chem., 2012, 77, 4466-4472.

A convenient copper-catalyzed decarboxylative direct cross-coupling of coumarin-/chromone-3-carboxylic acids with terminal alkynes provides functionalized 4-(aryl-/heteroaryl-ethynyl)chroman-2-ones and 2-(aryl-/heteroaryl-ethynyl)chroman-4-ones in good yields. This ligand- and base-free method offers a broad substrate scope and tolerates diverse functional groups.
A. Bhowmick, G. Brahmachari, Org. Lett., 2023, 25, 7095-7099.

Tetraethylammonium bromide catalyzes an intramolecular oxidative cyclization of O- or S-alkylated salicylic or thiosalicylic acid derivatives to access 4H-benzo[d][1,3]dioxin-4-ones or 4H-benzo[d][1,3]oxathiin-4-ones. While the reaction of salicylic acid derivatives proceeds through a radical pathway at 110 °C, the cyclization of the thiosalicylic acids runs at room temperature via an ionic pathway.
K. Manna, H. M. Begam R. Jana, Synthesis, 2023, 55, 1543-1552.

An effient tandem process consisting of palladium-catalyzed double-bond isomerization of long-chain olefins followed by intramolecular cyclization promoted by B₂(OH)₂ provides benzo-fused oxazaheterocycles. This strategy also provides rapid access to pyrido[3,4-b]indoles, trans-2-olefins, and enamides with high regio- and stereoselectivity.
L. Ding, Y.-N. Niu, X.-F. Xia, J. Org. Chem., 2021, 86, 10032-10042.

Phenols react with nitriles and dimethyl sulfoxide (DMSO) in the presence of a catalytic amount of (COCl)₂ in CH₃CN or chloroform to afford the corresponding N-acylbenzoxazines in good yields. DMSO acts as a source of HCHO, which is generated in situ.
H. Wang, Z. Xi, S. Huang, R. Ding, Y. Gao, Y. Liu, B. Sun, H. Tian, S. Liang, J. Org. Chem., 2021, 86, 4932-4943.

An Inverse Electron Demand Azo-Diels-Alder Reaction of o-Quinone Methides and Imino Ethers: Synthesis of Benzocondensed 1,3-Oxazines
D. V. Osipov, V. A. Osyanin, G. D. Khaysanova, E. R. Masterova, P. E. Krasnikov, Y. N. Klimochkin, J. Org. Chem., 2018, 83, 4775-4785.

Copper catalyzes a mild and operationally simple N-arylation of isatoic anhydrides with aryl(TMP)iodonium trifluoroacetates in good yields at room temperature. Alternative one-pot approaches for biologically relevant fenamic acid derivatives and N,N'-diarylindazol-3-ones are reported too.
R. A. Saikia, K. Talukdar, D. Pathak, B. Sarma, A. J. Thakur, J. Org. Chem., 2023, 88, 3567-3581.

A highly atom-efficient PIDA-mediated intramolecular iminoenol tautomer trapping reaction, followed by Et₃N-promoted aerobic oxidative ring construction enables the synthesis of multisubstituted 2-hydroxy-benzo[b][1,4]oxazins from N-(2-hydroxylaryl)enaminones at room temperature under air. O₂ serves as the oxygen source of the hydroxyl group.
H. Zhang, J. Shen, G. Cheng, Y. Feng, X. Cui, Org. Lett., 2018, 20, 664-667.

A base-catalyzed intramolecular defluorination/O-arylation of readily available α-fluoro-β-one-sulfones provides a series of 3-fluoro-1,4-oxathiine 4,4-dioxide derivatives in very good yields. This process is triggered by a catalytic amount of tetramethylguanidine (TMG) as base and molecular sieves as both an adsorbent to remove HF acid and an activator to assist C-F bond cleavage.
L. Kang, J. Zhang, H. Yang, J. Qian, G. Jiang, Synlett, 2021, 32, 785-789.

N-heterocyclic carbene/copper-cocatalyzed [4 + 3] annulations of salicylaldehydes with aziridines provide the corresponding 1,4-benzoxazepinones in good yields with exclusive regioselectivity.
Y.-F. Han, Z.-H. Gao, C.-L. Zhang, S. Ye, Org. Lett., 2020, 22, 8396-8400.

An atom-economic, efficient, rapid, and highly regioselective one-pot click reaction allows the synthesis of benzo[e][1,4]oxazepin-5-ones in excellent yields. The method involves epoxide ring-opening-ring-closing cascade with anthranilic acids using neat grinding at room temperature in the presence of lithium bromide as a mild catalyst. Pure products are obtained simply by washing the reaction mixture with warm water.
A. K. Singh, R. Chawla, L. D. S. Yadav, Synthesis, 2012, 44, 2353-2358.

Dehydration of 1,6-diols by treatment with BF₃·OEt₂ in dichloromethane gave tetrahydrobenzoxepines in very good yields, whereas 1,7-diols did not undergo dehydration.
M. Yus, T. Soler, F. Foubelo, Tetrahedron, 2002, 58, 7009-7016.

Benzo-fused sulfamate-derived imines readily react with glycine aldimino esters in the presence of an amine base to furnish 1,3-benzoxazepine frameworks in good yields.
M. K. Reddy, V. Bhajammanavar, M. Baidya, Org. Lett., 2021, 23, 3868-3872.

A chiral phosphoric acid catalyzes an intramolecular reaction of a range of benzylic alcohols bearing an internal oxetane to form chiral 1,4-benzodioxepines with high enantioselectivity. This oxetane desymmetrization process enables a direct synthesis of seven-membered heterocycles with good stereocontrol.
X. Zou, G. Sun, H. Huang, J. Wang, W. Yang, J. Sun, Org. Lett., 2020, 22, 249-252.

Ruthenium-catalyzed enyne metathesis of enynes connected with catechol, o-amino phenol, or o-phenylenediamine in DCM at room temperature overnight provides eight-membered ring compounds in high yield. In a similar manner, monocyclic 1,4-diaza- or 1-oxa-4-azacyclooctene can be synthesized.
M. Mori, T. Kitamura, N. Sakakibara, Y. Sato, Org. Lett., 2000, 2, 543-545.

A silver-catalyzed reaction between o-alkynylaryl aldehydes and trifluorodiazoethane provides trifluoromethylated benzo[d]oxepines. The reaction works through a silver-promoted 6-endo-dig cyclization of o-alkynylbenzaldehydes for the generation of an isochromenylium intermediate, followed by a ring-expansive addition of trifluorodiazoethane.
A. Dhami, S. P. Chandrasekharan, K. Mohanan, Org. Lett., 2023, 25, 3018-3022.

A visible-light photocatalytic aerobic oxidative lactonization of arene C(sp²)-H bonds provides benzocoumarin derivatives in good yields in the presence of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone and tert-butyl nitrite. This atom economic method offers mild reaction conditions, use of a green oxidant and metal-free catalysis.
Y. Wang, S. Wang, B. Chen, M. Li, X. Hu, B. Hu, L. Jin, N. Sun, Z. Shen, Synlett, 2020, 31, 261-266.

Iron photocatalysis enables a mild and efficient intramolecular aromatic C-H oxygenation of 2-biphenylcarboxylic acids to furnish benzocoumarins with a diverse array of substituents in very good yields.
S. Xia, K. Hu, C. Lei, J. Jin, Org. Lett., 2020, 22, 1385-1389.

DMAP catalyzes a sequential benzannulation and lactonization strategy of cyclic sulfamidate imines with δ-acetoxy allenoate as a 5C-synthon. This platform delivers π-extended coumarin frameworks under metal-free conditions via allylic elimination followed by Mannich coupling, proton shifts, C-N bond cleavage, and lactonization.
S. Chauhan, A. S. Kumar, K. C. K. Swamy, J. Org. Chem., 2023, 88, 12433-12444.

A direct Pd-catalyzed arylation reaction for the intramolecular formation of biaryl compounds using a novel phosphine ligand offers enhanced catalytic activity for transformations of previously unreactive substrates.
L.-C. Campeau, M. Parisien, M. Leblanc, K. Fagnou, J. Am. Chem. Soc., 2004, 126, 9186-9187.

A palladium-catalyzed cyclization reaction of phenols with trifluoromethyl-containing ortho-bromo-β-chlorostyrenes provides a variety of 6-trifluoromethyldibenzo[b,d]oxepines in good yields via O-alkenylation and subsequent C-H arylation.
Z.-Y. Zhao, X.-G. Zhang, H.-Y. Tu, J. Org. Chem., 2023, 88, 14242-14245.