Gas-phase thermolysis of t-butylsulfenamides: N,N-dimethyl t-butylsulfenamide, 2,6-dimethylpiperidinyl t-butylsulfenamide,and N-t-butyl t-butylsulfenamide

The amide derivatives of t-butylsulfenic acid mentioned in the title have been thermolyzed in a stirred-flow reactor at temperatures of 273–390°C and pressures of 7–15 torr, using toluene as carrier gas, at residence times of 0.4–2 s. Isobutene formed in 95–99% yields, through order one reactions, following the Arrhenius equations: N, N-dimethyl t-butylsulfenamide: These thermolyses are considered to take place through unimolecular, four-center cyclic transition-state reaction mechanisms, giving rise to isobutene plus the corresponding S-unsubstituted thiohydroxylamines. The latter decompose outside the reactor at temperatures above −78°C forming free sulfur and dimethylamine, 2,6-dimethylpiperidine, and t-butylamine, respectively. © 1996 John Wiley & Sons, Inc.     

Green procedure for highly efficient,rapid synthesis of imidazo[1,2-a]pyridine and its late stage functionalization

We unfold a rapid synthetic protocol for the preparation of imidazo[1,2-a]pyridine in cyclohexane. This methodology includes several advantages like shorter reaction time, catalyst free, broader substrate scope, and good yields of the desired products. Late stage functionalization of imidazo[1,2-a]pyridine has also been performed through C–H bond activation and C–C cross-coupling reactions.     

Stereoselective synthesis of the C-11 to C-19 segment of macrolactin 3 via a center inversion followed by Oxa-Michael addition approach

An efficient and short stereoselective synthesis of C11–C19 fragment of Macrolactin 3 was achieved. The vic-triol moiety (C15–C17) was derived from the C2–C4 chiral centers of D-mannose. The C-1 of D-mannose was utilized for the Wittig-olefination followed by hydroxylation using hydroboration reaction to introduce C11–C13 carbon chain in the C11–C19 fragment, whereas C5–C6 carbon chain of mannose was converted into C18–C19 of the target by dehydration reactions. Thus, the main strategy was (a) two consecutive Wittig-olefination reactions on C1 carbon of mannose, (b) inversion of C4 stereocenter, and (c) dehydration of C5–C6 vic-diol to olefin to result in the C11–C19 fragment.     

Thermal reactions of organyl chalcogenides with α,β-unsaturated aldehydes

Thermal gas-phase reactions of acrolein, cinnamaldehyde, and benzaldehyde with diorganyl chalcogenides and diorganyl dichalcogenides were studied. Acrolein does not react with chalcogenides at 300–600°C but completely decomposes under reaction conditions. At 600–650°C, cinnamaldehyde reacts only with diorganyl selenides and diselenides to give benzoselenophene. Its highest yield (53%) is achieved in the reaction with dimethyl diselenide at 630°C and at an equimolar ratio of the reactant. The gas-phase reactions of benzaldehyde at 400–500°C afford chalcogen-containing derivatives of several types, among which thioanisole and its selenium or tellurium analogs predominate. The mechanisms of the above reactions were discussed in terms of homolytic substitution of the formyl group at unsaturated carbon atoms by chalcogenyl radicals.     

Highly reusable support‐free copper(II) complex of para‐hydroxy‐substituted salen: Novel,efficient and versatile catalyst for C─N bond forming reactions

An air‐stable, highly active and versatile method for C─N bond forming reactions is reported. Under mild conditions using a highly reusable support‐free Cu(II)–salen complex, structurally diverse N ‐aryl‐substituted compounds were obtained via direct C─N bond forming reaction of HN‐heterocycles with aryl iodides or three‐component C─N bond forming reaction of 2‐bromobenzaldehyde, aniline derivatives and sodium azide in good to excellent yields. C─N bond forming reaction for benzimidazole derivatives was also performed in the presence of the catalyst under ambient conditions. A series of hybrid benzimidazoles bearing morpholine, tetrazole and quinoxaline backbones were produced using this method. All reactions were performed in short times under air. The Cu(II) catalyst could be reused up to eight times in the direct cross‐coupling reaction of 9H –carbazole with iodobenzene without any decrease in its catalytic activity.     

Divergent Coupling of Benzocyclobutenones with Indoles via C−H and C−C Activations

Highly selective divergent coupling reactions of benzocyclobutenones and indoles, in which the chemoselectivity is controlled by catalysts, are reported herein. The substrates undergo C2(indole)–C8(benzocyclobutenone) coupling to produce benzylated indoles and benzo[b]carbazoles in the Ni- and Ru-catalyzed reactions. A completely different selectivity pattern C2(indole)–C2(benzocyclobutenone) coupling to form arylated indoles is observed in the Rh-catalyzed reaction. Preliminary mechanistic studies suggest C−H and C−C activations in the reaction pathway. Synthetic utility of this protocol is demonstrated by the selective synthesis of three different types of carbazoles from the representative products.     

Integrated Micro Flow Synthesis Based on Sequential Br–Li Exchange Reactions of p‐, m‐, and o‐Dibromobenzenes

A micro flow system consisting of micromixers and microtube reactors provides an effective method for the introduction of two electrophiles onto p‐, m‐, and o‐dibromobenzenes. The Br–Li exchange reaction of p‐dibromobenzene with nBuLi can be conducted by using the micro flow system at 20 °C, although much lower temperatures (p‐bromophenyllithium was allowed to react with an electrophile in the micro flow system at 20 °C. The p‐substituted bromobenzene thus obtained was subjected to a second Br–Li exchange reaction followed by reaction with a second electrophile at 20 °C in one flow. A similar transformation can be carried out with m‐dibromobenzene by using the micro flow system. However, the Br–Li exchange reaction of o‐dibromobenzene followed by reaction with an electrophile should be conducted at ?78 °C to avoid benzyne formation. The second Br–Li exchange reaction followed by reaction with an electrophile can be carried out at 0 °C. By using the present method, a variety of p‐, m‐, and o‐disubstituted benzenes were synthesized in one flow at much higher temperatures than are required for conventional batch reactions.     

Cyclization reactions of 3-hydrazino[1, 2, 4]triazino[5, 6-b]indole

The reaction of 3-hydrazino[1, 2, 4]triazino[5, 6-b]indole I with nitrous acid affords the azide III which could be cyclized with acetic anhydride to 10-acetyl-10H-tetrazolo[5′,1′:3, 4][1, 2, 4]triazino[5, 6-b]indole IIb . Cyclization reactions of I with acetic anhydride, ethyl chloroformate, carbon disulphide and aromatic aldehydes to the corresponding fused triazolo derivatives V–VIII are reported. On the other hand cyclization reactions of I with malononitrile, ethyl cyanoacetate, ethyl acetoacetate and acetylacetone to the corresponding condensed pyrazolino derivatives IX–XI are also reported. The reaction of I with α-dicarbonyl compounds to form mono and dihydrazones are reported. The structure of the compounds prepared and their cyclization mechanisms are reported.     

Thermally stable polymers based on bismaleimides containing amide,imide, and ester linkages

Seven new structurally different bismaleimides were synthesized and characterized by infrared and proton nuclear magnetic resonance spectroscopy. The chain of these polymer precursors was extended by incorporating amidized, imidized, and esterified 4-chloroformyl phthalic anhydride. The bismaleimides containing amide and imide linkages were prepared by a simple synthetic route based on the reaction of the monomaleamic acid derived from various aromatic diamines (1 mol) with 4-chloroformyl phthalic anhydride (0.5 mol) and subsequent cyclodehydration of the intermediate triamic acid. In addition, chain extended bismaleimides were prepared by reacting the monomaleamic acid derived from p-phenylenediamine with several dianhydrides such as p-phenylene bis(trimellitamide anhydride), p-phenylene bis(trimellitate anhydride), and bis-phenol A bis(trimellitate anhydride). The differential thermal analysis scans of bismaleimides showed exotherms at 221–304°C associated with their polymerization reactions. The thermogravimetric analysis traces of polymers did not show a weight loss up to 351–393 and 344–372°C in N₂ and air atmospheres, respectively. The anaerobic char yield of polymers at 800°C was 44–61%. These polymers can be used for fabrication of composites having improved properties.     

Synthesis and Structure of Low‐valent η4‐Cinnamaldehyde Cobalt Complexes

Three η⁴‐(C=C–C=O) coordination cobalt(I) complexes 1 – 3 were synthesized by the reactions of cinnamaldehyde, p‐fluorocinnamaldehyde, and p‐chlorocinnamaldehyde with CoMe(PMe₃)₄. Complex 4 as η²‐(C=C) coordination was prepared by the reaction of chalcone with Co(PMe₃)₄. The structures of complexes 1 – 4 were confirmed by single‐crystal X‐ray diffraction. Although the reactions didn't undergo C–H bond activation and decarbonylation, the formation of complexes 1 – 4 deepens our understanding of the reactions between α,β‐unsaturated aldehyde or ketone with low‐valent central cobalt atom.     

Total Synthesis of the 7,10‐Epimer of the Proposed Structure of Amphidinolide N,Part I: Synthesis of the C1–C13 Subunit

Amphidinolide N, the structure of which has been recently revised, is a 26‐membered macrolide featuring allyl epoxide and tetrahydropyran moieties with 13 chiral centers. Due to its challenging structure and extraordinary potent cytotoxicity, amphidinolide N is a highly attractive target of total synthesis. During our total synthesis studies of the 7,10‐epimer of the proposed structure of amphidinolide N, we have synthesized the C1–C13 subunit enantio‐ and diastereoselectively. Key reactions include an l ‐proline catalyzed enantioselective intramolecular aldol reaction, Evans aldol reaction, Sharpless asymmetric epoxidation and Tamao–Fleming oxidation. To aid late‐stage manipulations, we also developed the 4‐(N‐benzyloxycarbonyl‐N‐methylamino)butyryl group as a novel ester protective group for the C9 alcohol.     

Synthesis of a poly(vinyl ether) containing a benzocyclobutene moiety and its reaction with dienophiles

1‐Benzocyclobutenyl vinyl ether (1) was easily prepared by the elimination reaction of hydrogen bromide from 1‐benzocyclobutenyl 1‐bromoethyl ether obtained by 1‐bromobenzocyclobutene and ethylene glycol via two steps in a good yield. Cationic polymerizations of 1 was carried out at −78°C for 2 h in toluene in the presence of BF₃OEt₂ as an initiator to give quantitatively the corresponding polymers (2) as white solids. As a model reaction of the polymer reaction of 2 with dienophiles, the Diels–Alder reactions of 1‐methoxybenzocyclobutene with maleic anhydride (MA) in toluene at 100–140°C for 3 h were carried out to obtain the corresponding Diels–Alder adduct quantitatively at 140°C. The polymer reactions of 2 with MA and N‐phenylmaleimide (MI) in toluene were carried out to yield the corresponding Diels–Alder adduct polymers in good yields. The degree of introduction of the dienophile could be controlled by temperature, and the unreacted benzocyclobutene moiety could further react with another benzocyclobutene moiety or dienophile. The properties (solubilities, T_g, and temperature of 10% weight loss) of the polymers obtained from the polymer reaction were quite different from those of 2. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 59–67, 1999     

[Au]/[Pd] Multicatalytic Processes: Direct One‐Pot Access to Benzo[c]chromenes and Benzo[b]furans

A new synthetic protocol that combines the advantages offered by eco‐friendly solvent‐free reactions and sequential transformations is reported. This strategy offers straightforward access to benzo[c]chromenes and benzo[b]furans from commercially available starting materials. This two‐step, one‐pot strategy consists of an Au‐catalyzed hydrophenoxylation process followed by Pd‐catalyzed C?H activation or Mizoroki–Heck reactions. The selectivity of the process towards C?H activation or Mizoroki–Heck reaction can be easily tuned.     

The kinetics of oxiranes addition to bis/2-hydroxyalkyl/disulfides and bis/2-hydroxyalkyl/sulfides in the presence of N,N-dimethylcyclohexylamine

Rate constants for the reaction of oxiranes with bis/2-hydroxyalkyl/disulfides, bis/2-Hydroxyalkyl/sulfides, and 1,6-Hexanediol in the presence of N,N-dimethylcyclohexylamine were studied at the temperature range of 50–90°C. A mechanism of these reactions has been proposed and its kinetic equation has been presented.     

Synthesis,functionalization and crosslinking reactions of poly(silylenemethylene)s

Novel poly(silylenemethylene)s have been prepared by the ring‐opening polymerization of 1,3‐disilacyclobutanes followed by a protodesilylation reaction with triflic acid. The silicon–aryl bond cleavage could be controlled by using different leaving groups, for instance phenyl‐ and para‐anisyl substituents. The reactions of the triflate derivatives with organomagnesium compounds, LiAlH₄, amines or alcohols gave functional substituted poly(silylenemethylene)s. Hydrosilylation reactions or reductive coupling with potassium–graphite led to organosilicon network‐polymers, which may serve as suitable precursors for silicon carbide and Si/C/N‐based materials. The structures of the polymers were identified by nuclear magnetic resonance spectroscopy (²⁹Si, ¹³C, ¹H). Copyright © 1999 John Wiley & Sons, Ltd.     

Mechanism and kinetics of the atmospheric degradation of perfluoropolymethylisopropyl ether by OH radical: a theoretical study

In the present work, the mechanism and kinetics of the reaction of perfluoropolymethylisopropyl ether (PFPMIE) with OH radical are studied. The reaction between PFPMIE and OH radical is initiated through breaking of C–C or C–O bond of PFPMIE. These reactions lead to the formation of COF₂ molecules and alkyl radical. The pathways corresponding to the reaction between PFPMIE and OH radical have been modelled using density functional theory methods M06-2X and MPW1K with 6-31G(d,p) basis set. It is found that the C–C bond breaking reaction is most favourable than the C–O bond breaking reaction. The subsequent reactions of the alkyl radicals, formed from the C–C bond breaking reactions, are studied in detail. The rate constant for the initial oxidation reactions is calculated using canonical variational transition state theory with small curvature tunnelling corrections over the temperature range of 278–350 K. From the calculated reaction, potential energy surface and rate constant, the lifetime and global warming potential of PFPMIE are studied.     

Terephthalic acid derived ligand‐stabilized palladium nanocomposite catalyst for Heck coupling reaction: without surface‐modified heterogeneous catalyst

A new protocol is reported for the synthesis of a heterogeneous palladium nanocomposite stabilized with a terephthalic acid‐derived ligand (N ,N ‐bis(4‐hydroxy‐3‐methoxybenzylidene)terephthalohydrazide). This is a highly insoluble ligand in common organic solvents, except dimethylformamide and dimethylsulfoxide. The resulting palladium nanocomposite acts as an efficient catalyst precursor for Mizoroki–Heck coupling reactions conducted under various reaction conditions. The spectral data suggest that the rate, yield and recycling of the catalyst are more effective for C–C coupling reactions. Copyright © 2016 John Wiley & Sons, Ltd.     

Electron transfer reactions between the superoxide ion and quinones

The electron transfer reactions of the superoxide ion with benzoquinone, trimethylbenzoquinone, and menadione in dimethylformamide were studied. A procedure of the determination of the relative rate constants of these reactions was developed; the reaction of O? ₂ with butyl bromide was chosen as a standard one. The relative rate constants measured at 20,°, 35°, and 50°C were slightly dependent on the quinone structure. The relationship between the free energy ΔF*of the electron transfer reactions and the standard free energy ΔF^o was discussed. This relationship is proposed as ΔF* = αΔF^o + β, where the proportionality coefficient α is equal to 0.04–0.11 for exothermal reactions and to 0.90–0.96 for endothermal reactions.     

Intramolecular,Stoichiometric (Li,Mg, Zn) and Catalytic (Ni,Pd, Pt) Metallo-Ene Reactions in Organic Synthesis [New Synthetic Methods (75)]

Metallo-ene reactions, hardly recognized until very recently, have experienced a breathtaking development when applied in an intramolecular sense. Efficient regio- and stereoselective magnesium-ene cyclizations have served as a cornerstone for numerous syntheses of structurally diverse natural products (e.g., sesquiterpenes of marine or plant origin, alkaloids, fragrances, insect defense compounds, and a fungitoxin). A brilliant example is the synthesis of the elusive odorant (+)-khusimone which outshines 20 years of work in the field of tricyclovetivane synthesis. Palladium-, platinum-, and nickel-catalyzed versions of the metallo-ene reaction are in a comparatively early stage of exploration, but, nevertheless, reveal intriguing potential. Hence an almost 100% stereospecific C? O→C? ;Pd-→ C? C chirality transfer permits simple and selective, cis- or trans-annelation processes. The mild cyclization conditions are compatible with various functional groups, such as nitrogen moieties, which offer interesting perspectives for the preparation of heterocycles (e.g., alkaloids) difficult to obtain by other methods. Carbon monoxide insertion reactions of the cyclized σ-metal intermediates were shown to afford annelated cyclopentanones and cyclopentenones with concomitant stereocontrolled formation of four carbon–carbon bonds. These and other observations, highlighted in this article, provide a platform for further extensions and applications of this powerful method in organic synthesis.     

V‐shaped graft copolymers via triple click reactions: Diels–alder,copper‐catalyzed azide–alkyne cycloaddition,and nitroxide radical coupling

We report here a simple and universal synthetic pathway covering triple click reactions, Diels–Alder, copper‐catalyzed azide–alkyne cycloaddition (CuAAC), and nitroxide radical coupling (NRC), to prepare well‐defined graft copolymers with V‐shaped side chains. The Diels–Alder click reaction between the furan protected‐maleimide‐terminated poly(ethylene glycol) (PEG) and a trifunctional core ( 1 ) carrying an anthracene, alkyne, and bromide was carried out to yield the corresponding α‐alkyne‐ and α‐bromide‐terminated PEG (PEG‐alkyne/Br) in toluene at 110 °C. Subsequently, the polystyrene or polyoxanorbornene with pendant azide functionality as a main backbone is reacted with the PEG‐alkyne/Br and 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO)‐terminated poly(ε‐caprolactone) using the CuAAC and NRC reactions in a one‐pot fashion in N,N′‐dimethylformamide at room temperature to result in the target V‐shaped graft copolymers. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4667–4674