Furan ring opening—indole ring closure: pseudooxidative furan ring opening in the synthesis of indoles

A new approach to the synthesis of 4-(2-indolyl)-3-buten-2-ones is described based on condensation of 2-tosylaminobenzyl alcohols with N-tosylfurfurylamine. Pseudooxidative furan ring opening occurred via protolytic elimination of tosylamide from the side chain of the 2-tosylaminoaryl(5-tosylaminomethylfur-2-yl)methanes formed in situ.     

Preparation of novel tricyclic ring systems containing the pyridazinone ring

Novel tricyclic ring systems, irmdazo[3,4-d]pyridazino[4,5-b][1,4]thiazines 3 , imidazo[2,1-b]pyridazino[4,5-e][1,3,4]thiadiazines 15 and 18 were prepared by the reaction of 5-amino-4-chloropyridazin-3(2H)-ones 1 and 5(4)-(1-methylhydrazino)-4(5)-chloropyridazin-3(2H)-ones 13 (16) with isothiocyanates 2 and 7 .     

New tellurium-containing ring systems

The recent discovery of a suitable synthesis of the monoanionic ditelluroimidodiphosphinate ligands [TePR₂NPR₂Te]⁻ (R = Ph, ⁱPr, ^tBu) has facilitated investigations of the fundamental chemistry of these chelating inorganic ligands. This article is focused on aspects of that chemistry in which the behaviour of this ditelluro PNP ligand differs from that of the well-studied dithio and diseleno congeners. The emphasis is on new tellurium-containing ring systems formed in: (a) redox transformations and (b) the synthesis of metal complexes.     

The unexpected conversion of a thiophene ring into a pyrrole ring via a putative nitrene intermediate

Triethylphosphite induced reductive cyclisation of 1-(2-nitrophenyl)-3,5-di(2-thienyl)pyrazole 6 afforded the expected 1,3-di(2-thienyl)pyrazolo[1,2-a]benzotriazole 7 (14%) together with an unexpected product which was shown to be a 2-(2-thienyl)pyrazolo[1,5-a]pyrrolo[2,1-c]quinoxaline 8 derivative (27%). A mechanism for the extrusion of sulfur during the transformation of heterocycle 6 into product 8 is proposed.     

Reactions expanding the aziridine ring

N-Phenylethyleneimine reacts with carbon dioxide to form 3-phenyl-2-oxazolidone. Carbon disulfide and carbon oxysulfide give poly(ethylene dithiocarbanilate) and poly(S-ethylene thiocarbanilate) which, on thermal decomposition, form 3-phenyl thiazolidine-2-thione and 3-phenyl-1, 3-thiazolid-2-one.     

A new approach to the nazarov reaction via sequential electrocyclic ring opening and ring closure

Regioselective dichlorocyclopropanation of 2-silyloxydienes furnishes vinylcyclopropanol silyl ethers in good yield. Treatment with silver(I) at room temperature effects disrotatory electrocyclic opening to a 2-chloro-3-silyloxypentadienyl cation, which then undergoes conrotatory (Nazarov) electrocyclization to provide chlorocyclopentenones. This two-step sequence offers a convenient and mild alternative to the standard Nazarov cyclization protocol via a formal 4+1 construction and furnishes products containing useful halogen functionality. In one case possessing a pendant phenyl group, interrupted Nazarov reaction to give a benzohydrindenone was observed.     

Chemoselective ring opening of benzoxazaphosphinines

Cyclization of 2-[(4-chloroanilino)methyl]phenol (1) with thiophosphoryl chloride afforded 2-chloro-3-(4-chlorophenyl)-3,4-dihydro-2H-1,3,2λ⁵-benzoxazaphosphinine-2-thione (2). Reaction of 2 with various heterocyclic amines (3) in the presence of Et₃N/NaH gave 3-(4-chlorophenyl)-2-nitrogen heterocyclic substituted-3,4-dihydro-2H-1,3,2λ⁵-benzoxaza-phosphinine-2-thiones (4). Further reaction of 4 with the N-sodium salt of amino heterocyclics in the presence of HCl at 50-60 °C opened the benzoxazaphosphinine ring chemoselectively at the endocyclic P-O bond and yielded 2-[4-chloro(heterocyclic substituted-phosphorothioyl)anilino]methylphenols 5-13.     

Competitive reaction pathways of C2Cl3 + NO via four-membered ring and bicyclic ring intermediates

The products and mechanisms of the atmospherically and environmentally important reaction, C(2)Cl(3) + NO, are investigated comprehensively by step-scan time-resolved Fourier transform infrared emission spectroscopy and the CCSD(T)/6-311+G(d)//B3LYP/6-311G(d) level of electronic structure calculations. Vibrationally excited products of Cl(2)CO, ClNCO, CCl(3)NCO and NCO have been observed in the IR emission spectra. Cyclic intermediates are found to play important roles leading to the rich variety of the chemical transformations of the reaction. Mainly two competitive reaction pathways are revealed: the four-membered ring intermediate pathway leading to the products Cl(2)CO + ClCN which is essentially barrierless and the bicyclic ring intermediate pathway leading to the product channels of ClNCO + CCl(2,) CCl(3)NCO and CCl(3) + NCO which is rate-limited by a barrier of 42.9 kJ mol(-1) higher than the reactants. By photolyzing the precursor at 248 and 193 nm, respectively, C(2)Cl(3) radicals with different internal energy are produced to observe the product branching ratios as a function of reactant energy. The Cl(2)CO channel via the four-membered ring intermediate pathway is shown to be overwhelmingly dominant at low energy (temperature) but become less important at high energy while the ClNCO and CCl(3)NCO channels via the bicyclic ring intermediate pathway are greatly enhanced and compete effectively. The experimental observation of the products and their branching ratios varying with reactant energy is well consistent with the calculated potential energy profiles.     

Mass spectral study of ring E of taraxasterol and compounds with similar ring substitution

The origin of the [M–69]⁺ and [M–111]⁺ signals in the mass spectrum of taraxasterol was studied through the use of C(18), (19), (21), (22) and/or (30) deuteriated derivatives. The generality of these signals for ring systems with an exocyclic methylene group and a methyl moiety on an adjacent carbon was verified with 2-methylmethylenecyclohexane, 1-methyl-2-methylene-trans-decalin, 1,10-dimethyl-2-methylene-trans-decalin and some of their deuteriated derivatives. The most plausible mechanism for the formation of the [M–69]⁺ ion appears to involve cleavage of both bonds allylic to the exocyclic methylene group with a 1,3-hydrogen transfer from the adjacent ring. Genesis of the [M–111]⁺ ion is more complicated but a five-membered allylic ion generated from ring D is proposed.     

Modeling furanose ring dynamics in DNA

Determination of the conformational flexibility of the furanose ring is of vital importance in understanding the structure of DNA. In this work we have applied a model of furanose ring motion to the analysis of deuterium line shape data obtained from sugar rings in solid hydrated DNA. The model describes the angular trajectories of the atoms in the furanose ring in terms of pseudorotation puckering amplitude (q) and the pseudorotation puckering phase phi. Fixing q, the motion is thus treated as Brownian diffusion through an angular-dependent potential U(phi). We have simulated numerous line shapes varying the adjustable parameters, including the diffusion coefficient D, pseudorotation puckering amplitude q, and the form of the potential U(phi). We have used several forms of the potential, including equal double-well potentials, unequal double-well potentials, and a potential truncated to "second order" in the Fourier series. To date, we have obtained best simulations for both equilibrium and nonequilibrium (partially relaxed) solid-state deuterium NMR line shapes for the sample [2' '-2H]-2'-deoxycytidine at the position C3 (underlined) in the DNA sequence [d(CGCGAATTCGCG)]2, using a double-well potential with an equal barrier height of U(0) = 5.5k(B)T ( approximately 3.3 kcal/mol), a puckering amplitude of q = 0.4 A, and a diffusion coefficient characterizing the underlying stochastic jump rate D = 9.9 x 10(8) Hz. Then the rate of flux for the C-D bond over the barrier, i.e., the escape velocity or the overall rate of puckering between modes, was found to be 0.7 x 10(7) Hz.     

N-heterocyclic carbene stabilized copper- and silver-phenylchalcogenolate ring complexes

The ligation of a N-heterocyclic carbene (NHC) to group 11 metal salts (Cu, Ag) was explored as an alternative to PR(3) ligands for the formation of copper- and silver-chalcogenolate cluster complexes. AgOAc and CuCl salts ligate with the NHC 1,3-di-isopropylbenzimidazole-2-ylidene ((i)Pr(2)-bimy) forming [Ag(OAc)((i)Pr(2)-bimy)] 1, [Ag(OAc)((i)Pr(2)-bimy)(2)] 2, [CuCl((i)Pr(2)-bimy)](2)3 and [CuCl((i)Pr(2)-bimy)(2)] 4 depending on the ratio of ligand to metal used. These have been characterized via spectroscopic and crystallographic methods. Complexes 1 and 3 were reacted with S(Ph)SiMe(3) and Se(Ph)SiMe(3) to form the polynuclear metal-chalcogenolates [Ag(4)(μ-EPh)(4)((i)Pr(2)-bimy)(4)] (5, E = S; 6, E = Se) and [Cu(3)(μ-EPh)(3)((i)Pr(2)-bimy)(3)] (7, E = S; 8, E = Se) in good yields. The structures of 5-8, as determined by single crystal X-ray crystallography, are described.     

Roof-shaped halide-bridged bimetallic complexes via ring expansion reaction

Binucleating behavior of rigid triptycene-based ligands has been studied. It has been demonstrated that trans-spanned transition-metal mononuclear complexes bearing 1,8-bis(diisopropylphosphino)triptycene (L1) and 1-diisopropylphosphino-8-diphenylphosphinotriptycene (L2) react with an appropriate transition-metal precursor via a ring-expansion pathway to form unusual bimetallic quasi-closed structures. New palladium and rhodium complexes featuring strongly bent (ca. 115 degrees ) M2(mu-Cl2) cores with very closely spanned metal centers (less than 3 A) have been prepared using the described ring-expansion reaction and have been fully characterized. Despite a constrained arrangement of the binuclear system, halogen bridges in all new compounds were stable in both the solid state and solution showing no tendency for dissociation even in the presence of added Lewis bases. Spontaneous resolution of the dissymmetric Pd2(mu-Cl)2Cl2(1-diisopropylphosphino-8-diphenylphosphinotriptycene) (2) into enantiopure antipodes is discussed as well.     

Introduction of the pyrazolidine ring into the pyrrole ring of indole

The reaction of indoles with 1-acyl-5-hydroxypyrazolidines under heterogeneous catalysis conditions leads, depending on the structure of indole, to 2- and/or 3-(1-acyl-5-pyrazolidinyl)indoles. Thus, the formation of 2-pyrazolidinylindoles is the results of an unco-substitution at the 3-position of the indole, followed by migration of the pyrazolidine ring.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1207–1213, September, 1990.     

A supramolecular hexameric ring from alumazene and methylsulfonate

A dealkylsilylation reaction of alumazene [2,6-(i-Pr)2C6H3NAlMe]3 (1) with trimethylsilyl methylsulfonate in a 1:2 molar ratio in toluene afforded a supramolecular cyclic hexamer {Me[2,6-(i-Pr)2C6H3NAl]3(O3SMe)2}6 (2) composed of six intact alumazene rings and possessing two types of bridging sulfonate groups. Changing the reagent molar ratio to 1:3 caused the third sulfonate to partially substitute the last alumazene methyl group in an eta2 fashion and introduced a disorder in the crystal lattice.     

Diode laser cavity ring down spectroscopy

We recently demonstrated how in cativy ring down spectroscopy (CRDS) a CW single frequency dye laser may be conveniently employed in place of the pulsed laser of standard CRDS. Here we extend this result to external cavity tunable diode lasers. Compact spectroscopic devices with extreme sensitivity (2 × 10⁻¹⁰/cm) become a reality. To demonstrate the instrumental resolution we obtained high quality NO₂ spectra in a supersonic slit jet, with a residual Doppler width of about 250 MHz.     

Reactions expanding the aziridine ring

Azirine reacts with 2-vinylpyridine in the presence of metallic sodium with the formation of N-[-(pyridin-2-yl)ethyl]azirine. The reaction of the latter with HBr and H₂S leads to N-(-bromoethyl)-and N-(-mercaptoethyl)-N-[-(pyridin-2-yl)ethyl]amines. Carbon oxysulfide and carbon disulfide react at room temperature with N-[-(pyridin-2-yl)ethyl]azirine to form copolymers in a ratio of 11. Carbon dioxide forms only N-[-(pyridin-2-yl)ethyl]-oxazolinone under similar conditions.For Communication IV, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1216–1218, September, 1973.     

Model of silicooxygen ring vibrations

In order to assign the bands in the IR spectra of silicates to the appropriate normal vibrations, a vibrational model has been proposed. A complex silicooxygen ring is considered as a ‘unit cell' composed of the appropriate number of [SiO₄]⁴⁻ tetrahedra. According to this model, in the ring silicates spectra we have to observe bands due to internal vibrations of individual tetrahedra and bands corresponding exclusively to the ring structure. Change in the tetrahedra symmetry from T_d (ideal tetrahedron) to C_2v (tetrahedron in a ring) and then to the ring symmetry: D_3h, D_4h and D_6h (ideal rings) with respect to reducible representations makes it possible to differentiate between the bands due to ring structure (pseudo-lattice vibrations) and internal modes of tetrahedra. It has been established that in the case of all ideal rings there is only one IR active vibrational mode, namely the one symmetric with respect to the axis of the highest fold, i.e. A₂″ in the case of 3-membered rings and A_2u in the case of 4- and 6-membered rings. The model proposed has been verified for different membered ring silicates.     

Electrophilic benzylation of 2-aminopyridine ring

In the reaction of 2-aminopyridine and its 3- or 5-methyl derivatives with benzyl chloride used in a molar ratio of 1:2, benzylation of 2-aminopyridine ring has been stated that 2-amino-3- or 5-benzylpyridines c as the major products were obtained. Formation of c type compounds took place in the decomposition of 2-benzylamino-3- or 5-benzylpyridines b obtained in the reaction of the 2-benzylaminopyridines a , excess benzyl chloride was used. Production of the b and c compounds, where the benzyl substituent occupied position 3 or 5 in 2-aminopyridine supported the electrophilic mechanism of the reaction (radical reaction was excluded). In the case of 2-aminopyridine and its 3-methyl derivative bis-(2-amino-5-pyridyl)phenylmethanes d were formed as the by-products.     

The oxetane ring in taxol

Numerous structure-activity studies combining synthesis and bioassay have been performed for the anti-cancer drug Taxol. The four-membered D-ring, an oxetane, is one of four structural features regarded to be essential for biological activity. This proposition is examined by application of a Taxol-epothilone minireceptor, K(i) estimation for microtubule binding and docking of Taxol analogues into a model of the Taxol-tubulin complex. In this way, we evaluate the two characteristics considered responsible for oxetane function: (1) rigidification of the tetracyclic Taxol core to provide an appropriate framework for presenting the C-2, C-4, C-13 side chains to the microtubule protein and (2) service as a hydrogen-bond acceptor. An energy decomposition analysis for a series of Taxol analogues demonstrates that the oxetane ring clearly operates by both mechanisms. However, a broader analysis of four-membered ring containing compounds, C- and D-seco derivatives, and structures with no oxetane equivalent underscores that the four-membered ring is not necessary for Taxol analogue bioactivity. Other functional groups and ligand-protein binding characteristics are fully capable of delivering Taxol biobehavior as effectively as the oxetane D-ring. This insight may contribute to the design and development of novel anticancer drugs.