Rh2(OAc)4 catalyzed substrate selective [4+2]/[2+2] cycloaddition of acylketenes: a highly chemo- and regioselective synthesis of spiro(oxindolyl)oxazinones and β-lactams

A rhodium(II) catalyzed [4+2]/[2+2] cycloaddition reaction of N-protected isatin-3-arylimine with acylketene derived from α-diazocarbonyl compounds has been achieved for the first time for the preparation of a novel class of spiro(oxindolyl)oxazinone and spiro(oxindolyl)-β-lactam derivatives.     

SOME REACTIONS OF 1,3-THIAZINE DERIVATIVES WITH ALIPHATIC DIAMINES

Abstract

A wide range of 2-substituted-5,6-dihydro-4H-1,3-thiazines (I) and tetrahydro-2H-1,3-thiazines (II) have been found to undergo a facile ring transformation reaction with aliphatic diamines to form the corresponding dinitrogen heterocycles (III) and (IV).     

Chemical Derivatization of Peptide Carboxyl Groups for Highly Efficient Electron Transfer Dissociation

The carboxyl groups of tryptic peptides were derivatized with a tertiary or quaternary amine labeling reagent to generate more highly charged peptide ions that fragment efficiently by electron transfer dissociation (ETD). All peptide carboxyl groups—aspartic and glutamic acid side-chains as well as C-termini—were derivatized with an average reaction efficiency of 99 %. This nearly complete labeling avoids making complex peptide mixtures even more complex because of partially-labeled products, and it allows the use of static modifications during database searching. Alkyl tertiary amines were found to be the optimal labeling reagent among the four types tested. Charge states are substantially higher for derivatized peptides: a modified tryptic digest of bovine serum albumin (BSA) generates ~90% of its precursor ions with z? > ?2, compared with less than 40 % for the unmodified sample. The increased charge density of modified peptide ions yields highly efficient ETD fragmentation, leading to many additional peptide identifications and higher sequence coverage (e.g., 70 % for modified versus only 43 % for unmodified BSA). The utility of this labeling strategy was demonstrated on a tryptic digest of ribosomal proteins isolated from yeast cells. Peptide derivatization of this sample produced an increase in the number of identified proteins, a >50 % increase in the sequence coverage of these proteins, and a doubling of the number of peptide spectral matches. This carboxyl derivatization strategy greatly improves proteome coverage obtained from ETD-MS/MS of tryptic digests, and we anticipate that it will also enhance identification and localization of post-translational modifications.

Transmetalation in the Suzuki–Miyaura Coupling: The Fork in the Trail

The Suzuki–Miyaura coupling is one of the few transition‐metal‐catalyzed C? C bond‐forming reactions that have been used in applications ranging from discovery chemistry to manufacturing processes. Although coupling proceeds through the generic three‐stage ‘oxidative addition, transmetalation, reductive elimination’ sequence, there are a number of features that differentiate the Suzuki–Miyaura process from other transition‐metal‐catalyzed cross‐couplings. Most of these features are centered around, or are a consequence of, activation of the boron reagent for transmetalation through one or both of two distinct pathways. This review focuses on the evidence that has been presented for this ‘fork in the trail′, and the potential to apply such mechanistic insight to the design of reaction conditions.     

Ultrasound‐Assisted Construction of Halogen‐Bonded Nanosized Cocrystals That Exhibit Thermosensitive Luminescence

Multi‐component organic nanocrystals that are comprised of two or more supramolecular building blocks can be used to extend the design and assembly scope of solid molecular materials. Herein, we report the use of ultrasonication to prepare halogen‐bonded stilbene‐based nano‐cocrystals that exhibit different photoemission properties, including one‐ and two‐phonon emission and fluorescence lifetimes, relative to those of macrodimensional crystals. The structural transformation from nano‐cocrystals into nanocrystals upon heating results in a luminescence red‐shift from greenish blue to yellow. The temperature‐dependent ratiometric luminescence may allow such nano‐cocrystals to be used as fluorescent sensors and thermosensitive materials.     

Macrocycle Dynamics in a Branched [8]Catenane Controlled by Three Different Stimuli in Three Different Regions

A branched [8]catenane from an efficient one-pot synthesis (72 % HPLC yield, 59 % isolated yield) featuring the simultaneous use of three kinds of templates and cucurbit[6]uril-mediated azide–alkyne cycloaddition (CBAAC) for ring-closing is reported. Design and assembly of the [8]catenane precursors are unexpectedly complex that can involve cooperating, competing and non-influencing interactions. Due to the branched structure, dynamics of the [8]catenane can be modulated in different extent by rigidifying/loosening the mechanical bonds at different regions by using solvent polarity, acid-base and metal ions as the stimuli. This work not only highlights the importance of understanding the delicate interplay of the weak and non-obvious supramolecular interactions in the synthesis of high-order [n]catenane, but also demonstrates a complex control of dynamics and flexibility for exploiting [n]catenanes applications.     

Keggin-type heteropoly-11-molybdo-1-vanadophosphoric acid supported montmorillonite K-10 clay-catalysed one-pot multi-component synthesis of chromeno[2,3-b]indoles

One-pot three-component synthesis of twelve different chromeno[2,3-b]indole derivatives were achieved by the condensation of β-naphthol, oxindole and various substituted aldehydes. Two more chromeno[2,3-b]indole derivatives were also synthesized through one-pot two-component condensation of salicylaldehyde with oxindole/chlorooxindole. Both the condensations were achieved by using Keggin-type heteropoly-11-molybdo-1-vanadophosphoric acid, H₄[PVMo₁₁O₄₀] supported on montmorillonite K-10 clay for about 10% as catalyst under environmentally benign solvent-free reaction condition. Shorter reaction time, excellent yield of product, sustainability of catalytic material and simple workup procedure under green experimental conditions are the advantages of this protocol.

     

Solar Hydrogen from an Aqueous,Noble‐Metal‐Free Hybrid System in a Continuous‐Flow Sampling Reaction System

We introduce the visible‐light photocatalytic H₂ evolution reaction as catalyzed by a cobaloxime/carbon nitride (C₃N₄) noble‐metal‐free hybrid photosystem by using a continuous‐flow sampling reaction system. The photocatalytic H₂ evolution rate is highly dependent on the structure of C₃N₄, in which porous C₃N₄ shows the best activity compared with bulk C₃N₄ (lamellar) and C₃N₄ nanosheets. When using porous C₃N₄, the system is neither affected by the solution pH, nor the C₃N₄ concentration, nor the structure of the cobaloxime complex.