Simple,Copper(I)-Catalyzed Oxidation of Benzylic/Allylic Alcohols to Carbonyl Compounds: Synthesis of Functionalized Cinnamates in One Pot

An environmentally benign [Cu(I)]-catalyzed oxidation of activated (benzylic/allylic) alcohols to the corresponding carbonyl compounds is presented. Interestingly, the reaction was also compatible with benzylic alcohols containing ortho-bromo substituents on the aromatic ring without competing with the expected intermolecular Buchwald coupling. Significantly, the catalytic system enables the synthesis of cinnamate-esters in a sequential domino one-pot fashion via oxidation followed by Wittig–Horner protocol.     

Synthesis of β‐Hydroxy α‐Sulfanyl Esters by Using Nanocrystalline Magnesium Oxide

Aldol‐type reaction between electron deficient aldehydes and sulfonium salts to afford the corresponding β‐hydroxy α‐sulfanyl esters in moderate‐to‐good yields by using nanocrystalline MgO is described. The sulfanyl group is a useful group for further transformations in organic synthesis. Low R_f‐value isomer is anti‐configured as revealed by X‐ray diffraction study and consistent with the assignment of ¹H‐NMR spectrum.     

Differentiation of diasteromeric α-sulfanyl-β-amino acid derivatives by electrospray ionization tandem mass spectrometry

A set of diastereomeric α-sulfanyl-β-amino acid derivatives, which are important building blocks for pharmaceuticals with potent biological activity, are studied by electrospray ionization tandem mass spectrometry. The collision induced dissociation (CID) spectra of [M+H](+), [M+NH(4)](+), [M+Na](+) and [M+Li](+) of the diastereomers were studied, among them the CID of [M+Na](+) and [M+Li](+) showed consistent differences in the relative abundance of characteristic ions that enabled distinction of the anti isomers from syn isomers. The decomposition pathways for the diagnostic ions were arrived at based on high-resolution mass spectrometry data, multiple mass spectrometry data, deuterium labeling experiments and the mass shift in accordance with the substituents located at different places. Loss of (R(1)-C(6)H(4)-CH=NH) and (Cat-NH-SO(2)R(2)) from [M+Cat](+), where Cat=Na and Li, and the product ions as a results of McLafferty rearrangement involving either >S=O or >C=O group were found to be diagnostic. The McLafferty rearrangement product ions involving >S=O group were more abundant in syn isomers while those involving >C=O group were more abundant in anti isomer. The selectivity observed in the decomposition of [M+Li](+) ions was found to be similar to that of [M+Na](+) ions, but in few cases the differences are marginal in the decomposition [M+Li](+) ions.     

Novel routes for the generation of structurally diverse labdane diterpenes from andrographolide

Andrographolide 1, the major constituent of the Indian medicinal plant Andrographis paniculata (Acanthaceae) was converted into the key intermediate 4 by selective oxidative degradation of the C-12,13 olefin bond. The aldehyde functional group present in 4 has been utilized for synthesizing a number of structurally diverse labdane diterpenes. Synthesis and in vitro cytotoxic activity results of the compounds prepared are discussed.     

Characteristics of La-modified Ni-Al2O3 and Ni-SiO2 catalysts for COx-free hydrogen production by catalytic decomposition of methane

Hydrotalcite precursors of La modified Ni-Al₂O₃ and Ni-SiO₂ catalysts prepared by co-precipitation method and the catalytic activities were examined for the production of CO_x-free H₂ by CH₄ decomposition. Physico-chemical characteristics of fresh, reduced and used catalysts were evaluated by XRD, TPR and O₂ pulse chemisorptions, TEM and BET-SA techniques. XRD studies showed phases due to hydrotalcite-like precursors in oven dried form produced dispersed NiO species upon calcination in static air above 450 °C. Raman spectra of deactivated samples revealed the presence of both ordered and disordered forms of carbon. Ni-La-Al₂O₃ catalyst with a mole ratio of Ni : La : Al = 2 : 0.1 : 0.9 exhibited tremendously high longevity with a hydrogen production rate of 1300 mol_H2 ·mol^?1_Ni. A direct relationship between Ni metal surface area and hydrogen yields was established.     

Characteristics of La-modified Ni-Al2O3 and Ni-SiO2 catalysts for COx-free hydrogen production by catalytic decomposition of methane

Hydrotalcite precursors of La modified Ni-Al2O3 and Ni-SiO2 catalysts prepared by co-precipitation method and the catalytic activities were examined for the production of COx-free H2 by CH4 decomposition. Physico-chemical characteristics of fresh, reduced and used catalysts were evaluated by XRD, TPR and O2 pulse chemisorptions, TEM and BET-SA techniques. XRD studies showed phases due to hydrotalcite-like precursors in oven dried form produced dispersed NiO species upon calcination in static air above 450 C. Raman spectra of deactivated samples revealed the presence of both ordered and disordered forms of carbon. Ni-La-Al2O3catalyst with a mole ratio of Ni : La : Al = 2 : 0.1 : 0.9 exhibited tremendously high longevity with a hydrogen production rate of 1300 molH2 mol 1 Ni. A direct relationship between Ni metal surface area and hydrogen yields was established.     

Bifunctional nanocrystalline MgO for chiral epoxy ketones via Claisen-Schmidt condensation-asymmetric epoxidation reactions

Design and development of a truly nanobifunctional heterogeneous catalyst for the Claisen-Schmidt condensation (CSC) of benzaldehydes with acetophenones to yield chalcones quantitatively followed by asymmetric epoxidation (AE) to afford chiral epoxy ketones with moderate to good yields and impressive ee's is described. The nanomagnesium oxide (aerogel prepared) NAP-MgO was found to be superior over the NA-MgO and CM-MgO in terms of activity and enantioselectivity as applicable in these reactions. An elegant strategy for heterogenization of homogeneous catalysts is presented here to evolve single-site chiral catalysts for AE by a successful transfer of molecular chemistry to surface metal-organic chemistry with the retention of activity, selectivity/enantioselectivity. Br?nsted hydroxyls are established as sole contributors for the epoxidation reaction, while they add on to the CSC, which is largely driven by Lewis basic O2-sites. Strong hydrogen-bond interactions between the surface -OH on MgO and -OH groups of diethyl tartrate are found inducing enantioselectivity in the AE reaction. Thus, the nanocrystalline NAP-MgO with its defined shape, size, and accessible OH groups allows the chemisorption of TBHP, DET, and olefin on its surface to accomplish single-site chiral catalysts to provide optimum ee's in AE reactions.     

Synthesis of α-amino nitriles through Strecker reaction of aldimines and ketoimines by using nanocrystalline magnesium oxide

Strecker reactions of various aldimines as well as ketoimines with TMSCN proceeded smoothly under mild conditions to give the corresponding α-amino nitriles and α,α-disubstituted α-amino nitriles, respectively, in good to excellent yields in the presence of nanocrystalline magnesium oxide. The reaction proceeds through hypervalent silicate species by coordination to O²⁻/O⁻ (Lewis basic site) of nanocrystalline magnesium oxide, proved by ²⁹Si NMR.     

[Cu]-catalyzed direct coupling of dibromoalkenes: Synthesis of symmetrical 1,3-diynes and triazoles

An efficient [Cu]-catalyzed homocoupling of 1,1-dibromoalk-1-enes is described for the synthesis of symmetrical 1,3-diyines. The method showed good substrate scope and amenable to aryl and heteroaryl systems. Significantly, the strategy was also successfully applied to the sequential one-pot synthesis of triazoles.