Regioselective synthesis of 1,4-disubstituted 1,2,3-triazoles via three-component coupling of secondary alcohols, TMSN3 and alkynes

1,4-Disubstituted 1,2,3-triazoles are obtained in excellent yields via a three-component coupling of secondary alcohols, alkynes and trimethylsilyl azide (TMSN₃). This one-pot reaction occurs through in situ generation of an azide from the alcohol and TMSN₃, followed by 1,3-dipolar cycloaddition of the terminal alkyne to afford the corresponding disubstituted triazoles.     

Cyclopentadienones as intermediates for the synthesis of highly functionalized biaryls

A new approach to the synthesis of substituted biaryls, via Diels-Alder reaction between cyclopentadienones and arylacetylenes, is described.     

Solid-phase synthesis of liquid crystalline isoxazole library

Combinatorial library of isoxazoles was prepared by 1,3-dipolar cycloaddition on solid support. p-Cyano derivatives showed nematic and/or smectic A phases. A bilayer smectic phase for 2h is proposed by the combination of molecular mechanics calculation and X-ray diffraction experiment.     

Photocycloaddition of Cyclohex‐2‐enones to Penta‐1,2,4‐triene

Dihydrothiinone 9a undergoes photocycloaddition regioselectively to all three C?C bonds of penta‐1,2,4‐triene ( 10 ), the relative stabilities of the biradical intermediates determining the product distribution. In contrast, cyclohexenone 9b and dihydropyranone 9c afford more complex mixtures of bicyclo[4.2.0]octanones, which also turn out to be less stable on chromatographic workup, reflecting the higher strain due to the shorter bond lengths (C? O and C? C vs. C? S) in the six‐membered rings, respectively.     

Polyalkoxybenzenes from plant sources 2. Synthesis of isoxazoline analogs of combretastatin from natural allyl(methylenedioxy)methoxybenzenes

A series of analogs of the natural mitostatic agent combretastatin were synthesized by the reaction of nitrile oxides with natural allylbenzenes, such as myristicin, apiol, and dillapiol. The 1,3-dipolar cycloaddition reactions in allylic systems proceed regiospecifically. The reactions with trans isomers of propenylbenzenes, viz., isomyristicin, isoapiol, and isodillapiol, as dipolarophiles produce regioisomers. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2375–2380, December, 2007.     

[2+2] Carbonylative cycloaddition catalyzed by palladium: stereoselective synthesis of β-lactams

[2+2] Carbonylative cycloaddition of chiral imines to various allyl halides, under CO pressure, in the presence of Et₃N, a catalytic amount of Pd(OAc)₂ and PPh₃ as ligand, are carried out. Separable diastereomeric mixtures of chiral alkenyl-β-lactams are isolated with good yields and high trans diastereoselections. Absolute configurations are assigned by X-ray measurements and ¹H NMR spectroscopy.     

多取代芳香族化合物的合成 5.卤素-苯硒基取代的丁二烯和丁炔二酸二甲酯的环加成-芳构化串连反应

本文报道用环加成－芳构化串连反应制备多取代芳香族化合物的方法。将１－氯－２－卤－３－苯硒基－１，３－丁二烯（５）与丁炔二酸二甲酯进行Ｄｉｅｌｓ－Ａｌｄｅｒ反应时，能直接生成多取代的芳香族化合物４－苯硒基－５－卤代邻苯二甲酸二甲酯（４）。若用２－卤素－３－苯硒基－１，３－丁二烯（１）与丁炔二酸二甲酯进行Ｄｉｅｌｓ－Ａｌｄｅｒ反应，只得到正常的加成产物４－苯硒基－５－卤素－１，４－环己二烯－１，２－二甲酸二甲酯（３），需再用ＤＤＱ处理，才得到多取代芳香族化合物（４）。     

Chemoselective synthesis of multiple epoxy-bridged tetrahydropyranone ring systems

Bis- as well as tris-tetrahydropyranone ring systems were obtained via multiple tandem cyclization-1,3-dipolar cycloaddition reactions of α-diazo ketones with ketone as well as aldehyde functional groups in a chemoselective manner.     

Studies towards the total synthesis of palau'amine. Formation of 4,5-dihydropyrrole-2-carboxylate intermediates by alkene-enamide ring-closing metathesis

A highly functionalized 4,5-dihydropyrrole-2-carboxylate is assembled by alkene-enamide ring-closing metathesis. Subsequent intramolecular azomethine imine dipolar cycloaddition provides a triazacyclopenta[cd]pentalene intermediate of potential use in a total synthesis of palau'amine.     

A Facile Synthesis of Indolizines by 1，3－Dipolar Cycloaddition of Pyridinium and Related Heteroaromatic Ylides with Alkenes in the Presence of TPCD，Py_4Co（HCrO_4）_2

ＡＦａｃｉｌｅＳｙｎｔｈｅｓｉｓｏｆｉｎｄｏｌｉｚｉｎｅｓｂｙ１，３－ＤｉｐｏｌａｒＣｙｃｌｏａｄｄｉｔｉｏｎｏｆＰｙｒｉｄｉｎｉｕｍａｎｄＲｅｌａｔｅｄＨｅｔｅｒｏａｒｏｍａｔｉｃＹｌｉｄｅｓｗｉｔｈＡｌｋｅｎｅｓｉｎｔｈｅＰｒｅｓｅｎｃｅｏｆＴＰ...