Double Heck Cross‐Coupling Reactions of Dibrominated Pyridines

Double Heck cross‐coupling reactions of 2,3‐ and 3,5‐dibromopyridine with various alkenes afforded the corresponding novel di(alkenyl)pyridines. The Heck reaction of 2,5‐dibromopyridine unexpectedly afforded 5,5′‐di(alkenyl)‐2,2′‐bipyridines by palladium‐catalyzed dimerization to give 5,5′‐dibromo‐2,2′‐bipyridine and subsequent twofold Heck reaction.     

Possible structural effect of a′,b′‐dihydroxyacetophenone units in the preformed oligoesters upon copolycondensation with isomeric c′,d′‐dihydroxyacetophenones by TsCl/dimethylformamide/pyridine

A two‐stage copolycondensation of a mixture of equal parts of isophthalic acid and terephthalic acid first with a′,b′‐dihydroxyacetophenone (a′,b′‐DHAP) and then with isomeric c′,d′‐DHAP was examined at 60 and 80 °C. A structurally selective reaction was observed. At 80 °C, the preformed oligomers from symmetrically substituted 2′,6′‐DHAP reacted better with similarly substituted 2′,6′‐ or 3′,5′‐DHAP to give the copolymers of significantly higher inherent viscosity values than from the reaction with asymmetrically substituted 2′,4′‐DHAP, whereas at 60 °C they did almost equally well with any c′,d′‐DHAP. Similarly, the reaction of oligomers from 2′,4′‐DHAP with asymmetrically substituted 2′,4′‐DHAP or 2,4‐dihydroxybenzophenone yielded better results than those from the reaction with 2′,6′‐ or 3′,5′‐DHAP at both temperatures. The copolycondensations with comonomers of the structure independent of DHAPs were not affected by the preformed oligomers from DHAPs. The results are discussed in terms of the distributions of resulting oligomers determined by gel permeation chromatography. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 616–623, 2003     

Novel regioselective synthesis of 3′H,4H‐spiro[chromene‐3,2′‐[1,3,4]thiadiazol]‐4‐one containing compounds

A variety of 3″,5″‐diaryl‐3″H,4′H‐dispiro[cyclohexane‐1,2′‐chromene‐3′,2″‐[1,3,4]thiadiazol]‐4′‐ones 3a‐c were synthesized regioselectively through the reaction of 4′H,5H‐trispiro[cyclohexane‐1,2′‐chromene‐3′,2″‐[1,3,4]oxadithiino[5,6‐c]chromene‐5″,1″′‐cyclohexan]‐4′‐one ( 1 ) with nitrilimines (generated in situ via triethylamine dehydrohalogenation of the corresponding hydrazonoyl chlorides 2a‐c ) in refluxing dry toluene. Single crystal X‐ray diffraction studies of 3a,b add support for the established structure. Similarly, 3′,5′‐diaryl‐2,2‐dimethyl‐3′H,4H‐spiro[chromene‐3,2′‐[1,3,4]thiadiazol]‐4‐ones 5a‐c were obtained in a regioselective manner through the reaction of 2,2,5′,5′‐tetramethyl‐4H,5′H‐spiro[chromene‐3,2′‐[1,3,4]oxadithiino[5,6‐c]chromen]‐4‐one ( 4a ) with nitrilimines under similar reaction conditions. On the other hand, reaction of 2,5′‐diethyl‐2,5′‐dimethyl‐4H,5′H‐spiro[chromene‐3,2′‐[1,3,4]oxadithiino‐[5,6‐c]chromen]‐4‐one ( 4b ) with nitrilimines in refluxing dry toluene afforded the corresponding 3′,5′‐diaryl‐2‐ethyl‐2‐methyl‐3′H,4H‐spiro[chromene‐3,2′‐[1,3,4]thiadiazol]‐4‐ones 5d‐f as two unisolable diastereoisomeric forms.     

An Efficient Synthesis of Spiro‐oxindole Derivatives by Three‐Component Reactions in Water

An efficient synthesis of (3S)‐1,1′,2,2′,3′,4′,6′,7′‐octahydro‐9′‐nitro‐2,6′‐dioxospiro[3H‐indole‐3,8′‐[8H]pyrido[1,2‐a]pyrimidine]‐7′‐carbonitrile is achieved via a three‐component reaction of isatin, ethyl cyanoacetate, and 1,2,3,4,5,6‐hexahydro‐2‐(nitromethylidene)pyrimidine. The present method does not involve any hazardous organic solvents or catalysts. Also the synthesis of ethyl 6′‐amino‐1,1′,2,2′,3′,4′‐hexahydro‐9′‐nitro‐2‐oxospiro[3H‐indole‐3,8′‐[8H]pyrido[1,2‐a]pyrimidine]‐7′‐carboxylates in high yields, at reflux, using a catalytic amount of piperidine, is described. The structures were confirmed spectroscopically (IR, ¹H‐ and ¹³C‐NMR, and EI‐MS data) and by elemental analyses. A plausible mechanism for this reaction is proposed (Scheme 2).     

Preparation of Partially Acetylated Carotenoids

Partially acetylated carotenoids were prepared from fully acetylated carotenoids by reaction with NaBH₄, and were characterized by UV/VIS, CD, ¹H‐NMR and mass spectra. The 3,6′‐diacetate, 3′,6′‐diacetate, and 6′‐acetate 10 – 12 , respectively, of (6′R)‐capsanthol (=(3R,3′S,5′R,6′R)‐β,κ‐carotene‐3,3′,6′‐triol; 4 ) were obtained from (6′R)‐capsanthol‐3,3′,6′‐triacetate ( 9 ), and the 3‐ and 3′‐acetates 13 and 14 , respectively, of 4 from (6′R)‐capsanthol 3,3′‐diacetate ( 8 ). The utility of this method was also demonstrated by the preparation of zeaxanthin and lutein monoacetates 16, 19 , and 20 .     

A Facile Synthesis of Oxoindenothiazine and Dioxospiro(indene‐2,4′‐thiazine) Derivatives from (Substituted ethylidene)hydrazinecarbothioamides

(E)‐2‐[2‐(1‐Substituted ethylidene)hydrazinyl]‐5‐oxo‐9b‐hydroxy‐5,9b‐dihydroindeno[1,2‐d][1,3]‐thiazine‐4‐carbonitriles and (E)‐5‐oxo‐[(E)‐(1‐substituted ethylidene)hydrazinyl]‐2,5‐dihydroindeno[1,2‐d][1,3]thiazine‐4‐carbonitriles have been obtained from the reaction of 2‐(substituted ethylidene)hydrazinecarbothioamides with 2‐(1,3‐dioxo‐2,3‐dihydro‐1H‐inden‐2‐ylidene)propanedinitrile ( 1 ) in ethyl acetate solution. However, (Z)‐6′‐amino‐1,3‐dioxo‐3′‐substituted‐2′‐[(E)‐(1‐phenylethylidene)hydrazono]‐1,2′,3,3′‐tetrahydrospiro(indene‐2,4′‐[1,3]thiazine)‐5′‐carbonitriles were observed during the reaction of N‐substituted‐2‐(1‐phenylethylidene)hydrazinecarbothioamides with ( 1 ). The structure assignment of products has been confirmed on the basis of ¹H‐, ¹³C‐NMR, and mass spectrometry, as well as theoretical calculations.     

Synthesis of (2′S)‐2′‐Deoxy‐2′‐C‐methylpurine Nucleosides and Their Phosphoramidites

We describe the stereoselective synthesis of (2′S)‐2′‐deoxy‐2′‐C‐methyladenosine ( 12 ) and (2′S)‐2′‐deoxy‐2′‐C‐methylinosine ( 14 ) as well as their corresponding cyanoethyl phosphoramidites 16 and 19 from 6‐O‐(2,6‐dichlorophenyl)inosine as starting material. The methyl group at the 2′‐position was introduced via a Wittig reaction (→ 3 , Scheme 1) followed by a stereoselective oxidation with OsO₄ (→ 4 , Scheme 2). The primary‐alcohol moiety of 4 was tosylated (→ 5 ) and regioselectively reduced with NaBH₄ (→ 6 ). Subsequent reduction of the 2′‐alcohol moiety with Bu₃SnH yielded stereoselectively the corresponding (2′S)‐2′‐deoxy‐2′‐C‐methylnucleoside (→ 8a ).     

Homologous SNV Reaction: Synthesis of l‐Methyl‐4‐[4′‐phenylsulfonyl‐1′,3′‐butadienyl]pyridinium Iodide and Its Reactivity with Thiol Groups Giving Rise to the Chromophoric Thioether

Thioether 4‐[(1′E,3′E)‐4′‐phenylsulfanyl‐1,3′‐butadienyl]pyridine 8 and sulfone 4‐(4′‐phenylsulfonyl‐1′,3′‐butadienyl)pyridine 14 were prepared by reaction of the carbanions derived from allylic thioether or allylic sulfone with isonicotinaldehyde. The reaction with the sulfonyl carbanion occurred at the α position and on heating the alcolate gave the dienic sulfone 14 . The corresponding pyridinium iodide 10 and 15 were prepared by reaction with methyl iodide, respectively, on pyridine derivates 8 and 14 . The dienic pyridinium thioether 10 showed a long wavelength absorption band centered at 420 nm. The reaction of dienic pyridinium sulfone 15 with thiophenol gave the dienic pyridinium thioether 10 by a nucleophilic vinylic substitution. The reaction of sulfone 15 with glutathione was of second order and the rate constant was 8.5 M^?1s^?1 at 30°C and pH 7, about 500 times smaller than the rate constant observed with (E)‐1‐methyl‐4‐(2‐methylsulfonyl‐1‐ethenyl)pyridinium iodide 1 . The dienic pyridinium thioether 10 was a negative solvatochrome.     

A Simple Way for Synthesis of Alkyne-Telechelic Poly(methyl methacrylate) via Single Electron Transfer Radical Coupling Reaction

The telechelic α,ω‐alkyne‐poly(methyl methacrylate) (alkyne‐PMMA‐alkyne) was synthesized by single electron transfer radical coupling (SETRC) reaction of α‐alkyne, ω‐bromine‐poly(methyl methacrylate) (alkyne‐ PMMA‐Br). The propargyl 2‐bomoisobutyrate (PgBiB) was first prepared to initiate atom transfer radical polymerization (ATRP) of methyl methacrylate at 45°C using CuCl/1,1,4,7,10,10‐hexamethyl triethylenetetramine (HMTETA) as homogeneous catalytic system. Then the SETRC reaction was conducted at room temperature in the presence of nascent Cu(0) and N,N,N′,N′ ′,N′ ′‐pentamethyldiethyllenetriamine (PMDETA). The precursor alkyne‐PMMA‐Br and coupled product alkyne‐PMMA‐alkyne were characterized by GPC and ¹H NMR in detail.     

An Efficient One‐Pot Synthesis of Bis Butenolides

3,3′,4,4′‐Tetramethyl‐5,5′‐dioxo‐2,2′‐bifuran‐2,2′(5H,5′H) diyl diacetate was obtained from the reaction between 2,3‐dimethyl maleic anhydride and acetic anhydride in the presence of zinc in toluene. This easy synthetic route gave bis butenolide in excellent yield.     

A Novel,One‐Pot Four‐Component Route to 2′‐Thioxo‐2′,3′‐dihydrospiro[indole‐3,6′‐[1,3]thiazin]‐2‐one Derivatives

An efficient route to 2′,3′‐dihydro‐2′‐thioxospiro[indole‐3,6′‐[1,3]thiazin]‐2(1H)‐one derivatives is described. It involves the reaction of isatine, 1‐phenyl‐2‐(1,1,1‐triphenyl‐λ⁵‐phosphanylidene)ethan‐1‐one, and different amines in the presence of CS₂ in dry MeOH at reflux (Scheme 1). The alkyl carbamodithioate, which results from the addition of the amine to CS₂, is added to the α,β‐unsaturated ketone, resulting from the reaction between 1‐phenyl‐2‐(1,1,1‐triphenyl‐λ⁵‐phosphanylidene)ethan‐1‐one and isatine, to produce the 3′‐alkyl‐2′,3′‐dihydro‐4′‐phenyl‐2′‐thioxospiro[indole‐3,6′‐[1,3]thiazin]‐2(1H)‐one derivatives in excellent yields (Scheme 2). Their structures were corroborated spectroscopically (IR, ¹H‐ and ¹³C‐NMR, and EI‐MS) and by elemental analyses.     

On the Reaction of Thiazole‐2,4‐diamines with Isothiocyanates – Preparation and Transformation of 2,4‐Diaminothiazole‐5‐carbothioamides

In the reaction of thiazole‐2,4‐diamines 8 with isothiocyanates 1 , 2,4‐diaminothiazole‐5‐carbothioamides 9, 10, 18 , and 19 as well as thiazolo[4,5‐d]pyrimidine‐7(6H)‐thiones 21 were formed. The carbothioamides 9, 10 , and 18 were transformed by reaction with different types of monofunctional and bifunctional electrophiles into hitherto unknown acceptor‐substituted 4,4′‐([2,5′‐bithiazole]‐2′,4′‐diyl)bis[morpholines] 24 and 29 , the 2′,4′‐bis(dialkylamino)[2,5′‐bithiazol]‐4‐(5H)‐ones 30 , and the 4‐substituted 2′,4′‐bis(dialkylamino)‐2,5′‐bithiazoles 31 . From 30 and 31 new 4‐mono‐ or 4,5‐disubstituted 2′,4′‐bis(dialkylamino)‐2,5′‐bithiazoles 34, 35, 38 , and 39 as well as 5‐substituted 2′,4′‐bis(dialkylamino)[2,5′‐bithiazol]‐4(5H)‐ones 33, 36 , and 37 were prepared.     

2,2‐Bis(methoxy‐NNO‐azoxy)ethyl Derivatives of 4,8‐Dihydro‐bis‐furazano[3,4‐b:3′4′‐e]pyrazine: The Synthesis and X‐ray Investigation

The first synthesis of 4,8‐dihydro‐bis‐furazano[3,4‐b:3′4′‐e]pyrazine bearing 2,2‐bis(methoxy‐NNO‐azoxy)ethyl groups has been developed. These compounds are obtained by aza‐Michael reaction of 1,1‐bis(methoxy‐NNO‐azoxy)ethene or its equivalents, such as 2,2‐bis(methoxy‐NNO‐azoxy)ethanol derivatives, with 4,8‐dihydro‐bis‐furazano[3,4‐b:3′4′‐e]pyrazine.     

A Facile synthesis of n,n′‐oligomethylenebis(4,5‐dihydrofuran‐3‐carboxamide)s using manganese(III)‐based radical cyclization of n,n′‐oligomethylenebis(3‐oxobutanamide)s with 1,1‐diarylethenes

The reaction of N,N′‐oligomethylenebis(3‐oxobutanamide)s with 1,1‐diarylethenes in the presence of manganese(III) acetate in acetic acid at 100° produced N N′‐oligomethylenebis(2‐methyl‐5,5‐diaryl‐4,5‐dihydrofuran‐3‐carboxamide)s. Similarly, the reaction of 3‐oxobutanamidoethyl 3‐oxobutanoate or N,N′‐(3,6‐dioxaoctamethylene)bis(3‐oxobutanamide) with 1,1‐diphenylethene gave (2‐methyl‐5,5‐diphenyl‐4,5‐dihydrofuran‐3‐amido)ethyl 2‐methyl‐5,5‐diphenyl‐4,5‐dihydrofuran‐3‐carboxylate or N,N′‐(3,6‐dioxa‐octamethylene)bis(2‐methyl‐5,5‐diphenyl‐4,5‐dihydrofuran‐3‐carboxamide) in moderate yields.     

Synthesis of 2,2′‐(p‐phenylene)bisbenzazoles compounds from terephthalohydroxamoyl chloride

In this study, synthesis of symmetric compounds of 2,2′‐(p‐phenylene)bisbenzothiazole, 2,2′‐(p‐phenyl‐ene)bisbenzimidazole and 5,5′‐dimethyl‐2,2′‐(p‐phenylene)bisbenzoxazole were benefited from the reaction of terephthalohydroxamoyl chloride with 2‐amino‐4‐methyl phenol, o‐aminothio phenol and o‐phenylenedi‐amin compounds. The structures of these compounds were confirmed by elemental analysis, mass, ¹H‐NMR and FT‐IR techniques.     

A Facile Synthesis of Enantiomerically Pure (R)‐6‐Arylbinols

This work reported a convenient method for the preparation of enantiomerically pure 6‐aryl‐2,2′‐dihydroxy‐1,1′‐binaphthyl derivatives starting from the commercially available (R)‐2,2′‐hydroxy‐1,1′‐binaphthyl [(R)‐ 1 ] via bromination, hydrolysis and Suzuki cross coupling reaction. This novel synthetic method was characterized with high regioselectivity, simple operation, mild reaction conditions, and excellent yield (up to 73%). On the other hand, we synthesized the target unknown compounds, which were confirmed by IR, ¹H NMR, ¹³C NMR, MS and elementary analysis.     

Structure of an unexpected trimer from the reaction of ageratochromene II with aluminum chloride

A new trimer from the reaction of ageratochromene [1] (6,7‐dimethoxy‐2,2‐dimethyl‐1‐benzopyran) with anhydrous aluminum chloride was shown to be 3,4‐dihydro‐6,7‐dimethoxy‐2,2‐dimethyl‐3‐(6′,7′‐dimethoxy‐2′,2′‐dimethyl‐2H‐1‐benzopyran‐4′‐yl)‐4‐(3′,4′‐dihydro‐6′, 7′‐dimethoxy‐2′,2′‐dimethyl‐2H‐1‐benzopyran‐3′‐yl)‐ 2H‐1‐benzopyran. Its structure was confirmed by NMR (¹H, ¹³C, DEPT‐135. COSY, HMBC, HSQC, TOCSY and NOESY), IR, mass spectra and elemental analysis. Copyright © 2002 John Wiley & Sons, Ltd.     

Efficient Automated Solid‐Phase Synthesis of DNA and RNA 5′‐Triphosphates

A fast, high‐yielding and reliable method for the synthesis of DNA‐ and RNA 5′‐triphosphates is reported. After synthesizing DNA or RNA oligonucleotides by automated oligonucleotide synthesis, 5‐chloro‐saligenyl‐N,N‐diisopropylphosphoramidite was coupled to the 5′‐end. Oxidation of the formed 5′‐phosphite using the same oxidizing reagent used in standard oligonucleotide synthesis led to 5′‐cycloSal‐oligonucleotides. Reaction of the support‐bonded 5′‐cycloSal‐oligonucleotide with pyrophosphate yielded the corresponding 5′‐triphosphates. The 5′‐triphosphorylated DNA and RNA oligonucleotides were obtained after cleavage from the support in high purity and excellent yields. The whole reaction sequence was adapted to be used on a standard oligonucleotide synthesizer.     

Synthesis of 1,3‐Selenazol‐2(3H)‐imines

The reaction of N,N′‐diarylselenoureas 16 with phenacyl bromide in EtOH under reflux, followed by treatment with NH₃, gave N,3‐diaryl‐4‐phenyl‐1,3‐selenazol‐2(3H)‐imines 13 in high yields (Scheme 2). A reaction mechanism via formation of the corresponding Se‐(benzoylmethyl)isoselenoureas 18 and subsequent cyclocondensation is proposed (Scheme 3). The N,N′‐diarylselenoureas 16 were conveniently prepared by the reaction of aryl isoselenocyanates 15 with 4‐substituted anilines. The structures of 13a and 13c were established by X‐ray crystallography.     

Synthesis and Asymmetric Enantioselective Addition of Chiral Polybinaphthyl and Polybinaphthol I.igands

Four chiral polymers P-1, P-2, P-3 and P-4 were synthesized by the polymerization of （S）-2,2＇-dioctoxy-1,1＇- binaphthyl-6,6＇-boronic acid （S-M-3） with （S）-6,6＇-dibromo-1,1＇-binaphthol （S-M-1）, （R）-6,6＇-dibromo-1,1＇- binaphthol （R-M-1）, （S）-3,3＇-diiodo-1,1＇-binaphthol （S-M-2） and （R）-3,3＇-diiodo-1,1＇-binaphthol （R-M-2） under Pd-catalyzed Suzuki reaction, respectively. All four polymers can show good solubility in some common solvents due to the nonplanarity of the polymers in the main chain backbone and flexible alkyl groups in the side chain. The analysis results indicate that specific rotation and circular dichroism （CD） spectral signals of the alternative S-S chiral polymers P-1 and P-3 are larger than those of S-R chiral polymers P-2 and P-4, but their UV-Vis and fluorescence spectra are almost similar. The results of asymmetric enantioselectivity of four polymers for diethylzinc addition to benzaldehyde indicate that catalytically active center is （R） or （S）-1, 1＇-binaphthol moieties.