Triflic acid-promoted aza-Prins-Ritter reaction sequence: a novel synthesis of 4-amidopiperidine derivatives

4-Amidopiperidine derivatives have been prepared for the first time in good yields and with high selectivity by means of aza-Prins-Ritter reaction sequence using 1.2 equiv of triflic acid under mild reaction conditions.     

Charge stabilization via electron exchange: excited charge separation in symmetric,central triphenylamine derived,dimethylaminophenyl–tetracyanobutadiene donor–acceptor conjugates

Photoinduced charge separation in donor–acceptor conjugates plays a pivotal role in technology breakthroughs, especially in the areas of efficient conversion of solar energy into electrical energy and fuels. Extending the lifetime of the charge separated species is a necessity for their practical utilization, and this is often achieved by following the mechanism of natural photosynthesis where the process of electron/hole migration occurs distantly separating the radical ion pairs. Here, we hypothesize and demonstrate a new mechanism to stabilize the charge separated states via the process of electron exchange among the different acceptor entities in multimodular donor–acceptor conjugates. For this, star-shaped, central triphenylamine derived, dimethylamine–tetracyanobutadiene conjugates have been newly designed and characterized. Electron exchange was witnessed upon electroreduction in conjugates having multiple numbers of electron acceptors. Using ultrafast spectroscopy, the occurrence of excited state charge separation, and the effect of electron exchange in prolonging the lifetime of charge separated states in the conjugates having multiple acceptors have been successfully demonstrated. This work constitutes the first example of stabilizing charge-separated states via the process of electron exchange.

The significance of electron exchange in stabilizing the charge-separated state is revealed in multi-modular donor–acceptor conjugates.     

Conditional VaR estimation using Pearson’s type IV distribution

This paper presents a new value at risk (VaR) estimation model for equity returns time series and tests it extensively on Stock Indices of 14 countries. Two most important stylized facts of such series are volatility clustering, and non-normality as a result of fat tails of the return distribution. While volatility clustering has been extensively studied using the GARCH model and its various extensions, the phenomenon of non-normality has not been comprehensively explored, at least in the context of VaR estimation. A combination of extreme value theory (EVT) and GARCH has been explored to analyze financial data showing non-normal behavior. This paper proposes a combination of the Pearson’s Type IV distribution and the GARCH (1, 1) approach to furnish a new method with superior predictive abilities. The approach is back tested for the entire sample as well as for a holdout sample using rolling windows.     

Towards the total synthesis of etnangien: synthesis of C32–C42 fragment by using a desymmetrization strategy

The construction of the C32–C42 fragment of etnangien is described using a desymmetrization strategy generating five stereogenic centers from a bicyclic lactone. Another notable feature includes the use of the Sharpless asymmetric epoxidation to generate a stereogenic center at C40.     

Preparation,spectral and structural characterization of (2-benzoylpyridine N(4)-methyl-N(4)-phenylthiosemicarbazonato) chloropalladium(II)

The synthesis, as well as spectral and structural characterization, of (2-benzoylpyridine-N(4)-methyl-N(4)-phenylthiosemicarbazonato)chloropalladium(II), [Pd(Bz4MePh)Cl], is described. The unit cell contains two crystallographically independent molecules [Pd(1)(Bz4MePh)Cl], (1), and [Pd(2)(Bz4MePh)Cl], (2), stabilized by intra- and intermolecular hydrogen bonding. The distance between the Pd(1) and Pd(2) centres is 3.5038(11) Å. The spectroscopic techniques used in this study are the following: u.v.-visible, i.r. and ¹H n.m.r. The protonation constants, determined spectrophotometrically, of the uncoordinated HBz4MePh are pK_a1 = 10.82 ± 0.03 and pK_a2 = 4.09 ± 0.02.     

Stereoselective total synthesis of (+)-strictifolione and (6R)-6-[(4R,6R)-4,6-dihydroxy-10-phenyldec-1-enyl]-5,6-dihydro-2H-pyran-2-one by Prins reaction and olefin cross-metathesis

Prins and olefin cross-metathesis reactions were used as the key steps for the stereoselective total synthesis of (+)-strictifolione and (6R)-6-[(4R,6R)-4,6-dihydroxy-10-phenyldec-1-enyl]-5,6-dihydro-2H-pyran-2-one. Removal of MOM protecting groups under neutral conditions using CeCl₃·7H₂O is an attractive addition to the present strategy.     

Ionic liquid accelerated intramolecular hetero-Diels-Alder reactions: a protocol for the synthesis of octahydroacridines

2-Azadienes derived in situ from arylamines and (R)-(+)-citronellal/3-methylcitronellal undergo intramolecular [4+2] hetero-Diels-Alder reactions in the air and moisture stable ionic liquid [bmim]BF₄ in the absence of any acid catalyst to afford 1,2,3,4,4a,9,9a,10-octahydroacridine derivatives in high to quantitative yields.