Selenopheno[3,2-c]- and [2,3-c]coumarins: Synthesis, cytotoxicity, angiogenesis inhibition, and antioxidant properties

Abstract

A B S T R A C TA simple method for the synthesis of substituted selenopheno[2,3-c] and -[3,2-c]coumarins by treatment of the corresponding ethynylcoumarins with in situ prepared selenium(IV) bromide in 1,4-dioxane-water was elaborated. Molecular structures for selected derivatives were confirmed by X-ray diffraction measurements. The cytotoxic activity of novel selenophenocoumarins showed higher activity and lower acute toxicity than sodium selenite on various tumor cell lines as well as an ability for inhibiting matrix metalloproteinases (MMP-1 -MMP-14), angiogenesis on matrigel in vitro and in vivo. The compounds exhibit antioxidant and prooxidant properties.

Construction of a Functionalized Selenophene‐Allylidene Ligand via Alkyne Double Action at a Diiron Complex

“…The µ‐CO ligand shows a considerable asymmetry [Fe(1)–C(12) 1.981(5) Å, Fe(2)–C(12) 1.902(5) Å], as a consequence of the more π‐acidic terminal CO ligand on Fe(1) with respect to the η 3 ‐allylidene ligand on Fe(2). The selenophene ring is perfectly planar [mean deviation from the Se(1)–C(2)–C(1)–C(4)–C(5) least‐squares plane 0.0159 Å] and the bonding parameters are comparable to those available for analogous hetero‐cyclic systems , . The C(1)–N(1) distance [1.419(6) Å] is typical for a C(sp 2 )–N single bond, as also suggested by the sum of the angles at N(1) [346.5(7)°], which indicates a sp 3 rather than sp 2 hybridization of nitrogen.…”

“…The structure of 6a was ascertained by single‐crystal X‐ray diffraction (Figure , Table ). It consists of a cis ‐[Fe 2 Cp 2 (CO)(µ‐CO)] core, to which is (µ‐η 1 :η 3 )‐coordinated an allylidene ligand functionalized with a very rare example of multi‐substituted 3‐amino‐selenophene , …”

Synthetic Routes to Coumarin(Benzopyrone)-Fused Five-Membered Aromatic Heterocycles Built on the α-Pyrone Moiety. Part 1: Five-Membered Aromatic Rings with One Heteroatom

“…A few articles have discussed the possibility of synthesizing the fused selenophen-chromen-(benzopyran)-4-one moiety. A simple method for the synthesis of substituted 4 H -selenopheno[2,3- c ] benzopyran-4-ones 108 is by the treatment of 3-ethynylcoumarins 107 with selenium (IV) oxide and concentrated hydrobromic acid at room temperature [ 16 , 95 ]. Similarly, 4 H -selenopheno-[3,2- c ]benzopyran-4-ones 111 was prepared under the same conditions using 4-ethynylcoumarins 110 .…”

“…Coumarins are a family of benzopyrones (1,2-benzopyrones or 2 H -[1]benzopyran-2-ones), which represent an important family of oxygen-containing heterocycles, widely distributed in nature [ 1 , 2 , 3 , 4 ]. Coumarins display a broad range of biological and pharmacological activities, [ 5 , 6 ] such as antiviral [ 7 , 8 , 9 , 10 ], anticancer [ 11 , 12 , 13 ], antimicrobial [ 14 , 15 ], and antioxidant [ 16 , 17 , 18 ] activities. On the other hand, coumarin represents an ingredient in perfumes [ 19 ], cosmetics [ 20 ], and as industrial additives [ 21 , 22 ].…”

Iron‐Mediated Cyclization of 1,3‐Diynyl Propargyl Aryl Ethers with Dibutyl Diselenide: Synthesis of Selenophene‐Fused Chromenes

“…Thus, we reported, in the present study, a route to obtain selenophene‐fused chromene derivatives 2 through the cascade cyclization of 1,3‐diynyl propargyl aryl ethers 1 promoted by iron(III) salt and diorganyl diselenides (Scheme ). Particularly, the selenophene‐fused chromenes have attracted our attention because of their cytotoxic activity against various tumor cell lines, in vitro and in vivo anti‐angiogenic, antioxidant, and prooxidant properties . Whereas the synthesis of furan‐fused chromenes and thiophene‐fused chromenes is widespread in the literature, the preparation of 1‐(organoselenyl)‐selenophene‐fused chromenes is not reported.…”