A facile route to 1,5‐benzodiazepin‐2‐yl‐phosphonates via ytterbium chloride‐catalyzed three‐component reaction

1,5‐Benzodiazepin‐2‐yl‐phosphonates were facilely synthesized via a one‐pot three‐component condensation of o‐diaminobenzene, 1,3‐diketone and diethyl phosphite in the presence of a catalytic amount of ytterbium chloride under mild reaction conditions. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:89–95, 2010; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20573     

A facile synthesis of fluorine‐containing heterocycles ‐ use of 1,1,1‐trifluoro‐2‐alkanones as a convenient synthetic intermediate

1,1,1‐Trifluoro‐2,3‐alkanediones 2 easily obtainable from various aldehyde dialkylhydrazones were reacted with several diamines to afford trifluoromethylquinoxalines 3 and trifluoromethylpyrazines 4 in good yields. With the use of aldehydes and aqueous ammonia instead of diamines, diketones 2 were successfully converted to the corresponding 4‐trifluoromethylimidazoles 5 in satisfactory yields.     

A novel synthetic route to N‐protected 1‐aminoalkylphosphonates

Dialkyl and dithioalkyl N‐protected 1‐aminoalkylphosphonates were synthesized using reactions of benzyl carbamate, aldehydes and chlorophosphites, or dithioalkyl chlorophosphite, respectively. This represents a novel synthetic method for 1‐aminoalkylphosphonates. © 2000 John Wiley & Sons, Inc. Heteroatom Chem 11:417–421, 2000     

A facile synthesis of 2‐amino‐1,3‐selenazole by reaction of N,N‐unsubstituted selenourea with ketone

2‐Dialkylamino‐1,3‐selenazoles were yielded by the reaction of N,N‐unsubstituted selenoureas with ketones in the presence of ferric chloride. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:88–92, 2006; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20180     

A facile one‐pot synthesis of novel substituted 1,2,3,4‐tetrahydropyrimidines

A facile one‐pot synthesis of 5‐benzoyl‐6‐methylthio‐1,2,3,4‐tetrahydropyrimidines in good yields is reported.     

1,N6‐Etheno derivative of 7‐de­aza‐2,8‐di­aza­adenosine

In the tricyclic nucleoside 7‐(β‐d ‐ribo­furan­osyl)‐7H‐imidazo­[1,2‐c]­pyrazolo­[4,3‐e][1,2,3]­triazine, C₁₁H₁₂N₆O₄, the con­formation of the N‐gly­cosyl bond is intermediate between anti and high anti [χ = −103.5 (3)°]. The ribo­furan­ose moiety adopts a ₃T² sugar pucker (S‐type sugar) and the conformation at the exocyclic C—C bond is ap (gauche–trans). Molecules of the title compound form a three‐dimensional network via three medium–strong intermolecular hydrogen bonds (one O—H⋯N and two O—H⋯O bonds).     

A facile synthesis of 1‐alkyl‐5‐arylalkoxy‐6‐methoxy‐3,4‐dihydroisoquinolines

1‐Alkyl‐5‐arylalkoxy‐6‐methoxy‐3,4‐dihydroisoquinolines were synthesized by the alkylation of 1‐alkyl‐5‐hydroxy‐6‐methoxy‐3,4‐dihydroisoquinolines with arylalkyl halide in the presence of potassium carbonate. 1‐Alkyl‐5‐hydroxy‐6‐methoxy‐3,4‐dihydroisoquinolines as key precursor prepared from o‐vaniline via 6 steps.     

A facile and convenient synthesis of tetrasubstituted N‐hydroxypyrroles via intramolecular wittig reaction

Treatment of triphenylphosphine with dialkyl acetylenedicarboxylate leads to 1:1 adduct and concomitant protonation of late adduct by pentan‐2,3,4‐trione 3‐oxime gave the reactive intermediate, vinyltriphenylphosphonium salts, which undergoes an intramolecular Wittig reaction to produce tetrasubstituted N‐hydroxypyrroles in fairly high yields. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:100–103, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20382     

A facile synthesis of novel thiazolo[4,5‐d]pyrimidin‐7‐ones

Sixteen 5‐alkylamino‐3,6‐diaryl‐2‐thioxo‐2,3,6,7‐tetrahydrothiazolo[4,5‐d]pyrimidin‐7‐ones 4a , 4b , 4c , 4d , 4e , 4f , 4g , 4h , 4i , 4j , 4k , 4l , 4m , 4n , 4o , 4p were designed and easily synthesized via a tandem aza‐Wittig reaction. The iminophosphorane 2 , obtained from reaction of 1 with triphenylphosphine, hexachloroethane and Et₃N, reacted with aromatic isocyanate to give carbodiimide 3 . carbodiimide 3 reacted with alkylamines to provide the title compounds in 45–61% isolated yields in presence of catalytic amount of ethoxide. The structures of compounds 4 were confirmed by ¹H NMR, IR, MS, and elemental analysis. J. Heterocyclic Chem., 2011.     

A facile synthesis of cytogenin (8‐hydroxy‐3‐hydroxymethyl‐6‐methoxyisocoumarin)

A facile and straightforward synthesis of cytogenin 1 (8‐hydroxy‐3‐hydroxymethyl‐6‐methoxyisocoumarin) metabolite of Streptoverticillium eurocidicum and Certocystis fimbriata has been achieved. Condensation of chloroacetyl chloride with 3,5‐dimethoxyhomophthalic acid 2 directly furnished 3‐chloromethyl‐6,8‐dimethoxyisocoumarin 3 which was hydrolyzed to 6,8‐dimethoxy‐3‐hydroxymethylisocoumarin 4 using 0.05% aqueous sodium hydroxide in THF. Regioselective demethylation of 4 yielded cytogenin 1 . In model experiments, 3‐chloromethylisocoumarin was prepared and converted into 3‐hydroxymethyl isocoumarin.     

A facile route to ureidopyrimidinone‐functionalized polymers via RAFT

Three new ureidopyrimidinone(UPy)‐functionalized chain‐transfer agents (CTAs) have been synthesized for use in reversible addition‐fragmentation chain transfer (RAFT) polymerization. These UPy‐CTAs are able to polymerize a wide variety of vinyl monomers to yield UPy‐functionalized polymers, including homopolymers, block copolymers, and amphiphilic block copolymers. These polymers have been characterized via ¹H and ¹³C NMR spectroscopy, gel permeation chromatography (GPC), UV/visible spectroscopy and differential scanning calorimetry (DSC) to demonstrate end‐group fidelity. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

A convenient synthetic route to mannose 6‐phosphonate—cholesteryl conjugate

A multistep synthesis of a mannose 6‐phosphonate‐based glycolipid is described involving (1) a one‐carbon chain elongation at the 6‐position of mannose, followed by (2) phosphonation, using tris(trimethylsilyl)phosphite. This method was shown to e efficient and provides a general route to various mannose 6‐phosphonate‐based compounds for the design of drug delivery systems. © 2003 Wiley Periodicals, Inc. Heteroatom Chem 14:241–246, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10134     

A facile route for the synthesis of novel γ‐lactams

A selective reduction and its subsequent cyclisation of novel isoxazolidines into γ‐lactams have been examined in presence of Raney ‐ nickel catalyst.     

Theoretical and synthetic approach to novel spiroheterocycles derived from isatin derivatives and L‐proline via 1,3‐dipolar cycloaddition

A cyclic secondary α‐amino acid, viz. L ‐proline, reacts with isatin derivatives via decarboxylative azomethine ylide formation and subsequent cycloaddition with various dipolarophiles to give cycloadducts in moderate to good yield. Theoretical studies have been performed to study the stereochemistry of the products formed. © 2003 Wiley Periodicals, Inc. Heteroatom Chem 14:36–41, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10063     

A facile synthesis of 4‐, 6‐ and 7‐formyl‐1H‐indole‐2‐carboxylates: The CH2SO3H functionality as a masked formyl group

The valuable new synthetic intermediates, ethyl 4‐, 6‐ and 7‐formyl‐1H‐indole‐2‐carboxylates ( 10, 11, 12 ) were prepared from 2‐ethoxycarbonyl‐1H‐indole‐4‐, 6‐ and 7‐methanesulfonic acids ( 1, 2, 3 ), respectively. The transformation of sulfomethyl group to formyl function was accomplished through elimination of SO₂ to yield ethyl 4‐, 6‐ and 7‐chloromethyl‐1H‐indole‐2‐carboxylates ( 4, 5, 6 ), hydrolysed to ethyl 4‐, 6‐ and 7‐hydroxymethyl‐1H‐indole‐2‐carboxylates ( 7, 8, 9 ), then oxidized to aldehydes ( 10, 11, 12 ). Protection at N1 of indole was not necessary. A marked increase in the rate of hydrolysis of 7‐chloromethyl‐indoles compared to that of 4‐ and 6‐(chloromethyl)indoles was observed.     

A novel shape memory poly(ε‐caprolactone) network via UV‐triggered thiol‐ene reaction

A facile method to prepare shape memory polymers crosslinked by SiO₂ is described. A series of biodegradable shape memory networks were obtained through thiol‐ene reaction triggered by UV irradiation between surface‐thiol‐modified SiO₂ nanoparticles and end‐acrylate poly (ε‐caprolactone) (PCL). The highly selective thiol‐ene reaction ensured a uniform distribution of PCL chains between crosslinkers, contributing well‐defined network architecture with enhanced mechanical and shape‐memory properties. Thiol‐functionalized silica nanoparticle was characterized by using FTIR and XPS analysis, and ¹H NMR spectra was used to confirm the successful modification of terminal hydroxyl group of PCL diol. Surface‐modified silica particles were found well dispersible in acrylate‐capped PCL supported by SEM. Thermal and crystalline behaviors of the obtained polymers were analyzed by DSC and XRD, and DMA measurement proved good mechanical property. The shape memory behavior and tensile strength was somewhat tunable by the length of PCL. Acceptably, sample SiO₂‐SMP2k presented 99% recovery ratio and 97% shape fixity, and its relatively high tensile strength showed an attractive potential for biomedical application. Finally, a possible molecular mechanism accounting for the shape memory property was illustrated. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 692–701     

6‐Polyfluoroacyl‐ and 6‐trichloroacetylnorkhellins: Synthesis and reaction with aromatic amines

Five new 6‐polyhaloacylnorkhellins were synthesized in high yields from diethoxymethyl acetate and the condensation products of khellinone with R_FCO₂Et and CCl₃COCl. Reaction of 6‐polyfluoroacylnorkhellins with primary aromatic amines yielded 6‐(arylaminomethylene)‐7‐hydroxy‐4,9‐dimethoxy‐7‐(polyfluoroalkyl)furo[3,2‐g]chroman‐5‐ones. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:99–103, 2006; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20174