: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

140 years ago Adolf von Baeyer proposed the structure of a heteroaromatic compound which revolutionized organic and medical chemistry: indole. After more than a century, indole itself and the complexity of naturally occurring indole derivatives continue to inspire and influence developments in synthetic chemistry. In particular, the ubiquitous presence of indole rings in pharmaceuticals, agrochemicals, and functional materials are testament to the ever increasing interest in the design of mild and efficient synthetic routes to functionalized indole derivatives. This Review emphasizes the achievements in the selective catalytic functionalization of indoles (C-C bond-forming processes) over the last four years.

Catalytic Functionalization of Indoles in a New Dimension

In 2008, we published the first set of guidelines for standardizing research in autophagy. Since then, this topic has received increasing attention, and many scientists have entered the field. Our knowledge base and relevant new technologies have also been expanding. Thus, it is important to formulate on a regular basis updated guidelines for monitoring autophagy in different organisms. Despite numerous reviews, there continues to be confusion regarding acceptable methods to evaluate autophagy, especially in multicellular eukaryotes. Here, we present a set of guidelines for investigators to select and interpret methods to examine autophagy and related processes, and for reviewers to provide realistic and reasonable critiques of reports that are focused on these processes. These guidelines are not meant to be a dogmatic set of rules, because the appropriateness of any assay largely depends on the question being asked and the system being used. Moreover, no individual assay is perfect for every situation, calling for the use of multiple techniques to properly monitor autophagy in each experimental setting. Finally, several core components of the autophagy machinery have been implicated in distinct autophagic processes (canonical and noncanonical autophagy), implying that genetic approaches to block autophagy should rely on targeting two or more autophagy-related genes that ideally participate in distinct steps of the pathway. Along similar lines, because multiple proteins involved in autophagy also regulate other cellular pathways including apoptosis, not all of them can be used as a specific marker for bona fide autophagic responses. Here, we critically discuss current methods of assessing autophagy and the information they can, or cannot, provide. Our ultimate goal is to encourage intellectual and technical innovation in the field.

Guidelines for the use and interpretation of assays for monitoring autophagy (4th edition)

10. Patented Literature 2616 10.1. Esterification 2616 10.2. Ether Formation 2619 10.2.1. Etherification without Cyclization 2619 10.2.2. Etherification with Cyclization 2624 10.3. N-Alkylation 2625 10.4. Other Reactions 2627 11. Summary and Outlook 2628 12. Note Added in Proof 2628 13. Abbreviations Used in This Review 2629 14. Acknowledgments 2629 15. Supporting Information Available 2630 16. References 2630

Mitsunobu and Related Reactions: Advances and Applications

Additions of Organometallic Reagents to C=N Bonds: Reactivity and Selectivity

Convenient procedures for the chemo- and diastereoselective reduction of β-enamino esters (1) are described. Both cis- and trans-γ-amino al- cohols (2) or β-amino esters (3) can be prepared by reduction of β-ena- mino esters (1), readily available starting materials, with the use of inexpensive reagents Na/i-PrOH or NaHB(OAc) 3 /AcOH, respectively, and the appropriate reduction conditions. The mechanisms and diastereosele- ctivities for the reductions are discussed. The relative configurations and conformations of the diastereoisomeric γ-amino alcohols (2) and β- amino esters (3) obtained are established by 1 H and 13 C NMR study and unequivocally set by their cyclic derivatives tetrahydro-1,3-oxazines (4)

Chemo- and Diastereoselective Reduction of .beta.-Enamino Esters: A Convenient Synthesis of Both cis- and trans-.gamma.-Amino Alcohols and .beta.-Amino Esters

Alkylation of indoles by means of the Michael addition has been the subject of a number of investigation. It is well established that regioselectivity in the additions of indoles to electron-deficient alkenes is strongly controlled by the reaction medium. In a continuation of the work on developing greener and cleaner technologies, the cerium(III) chloride heptahydrate and sodium iodide combination supported on silica gel catalyzes the alkylation of various indoles with α,β-unsaturated ketones giving 3-(3-oxoalkyl)indole derivatives in good yields. The substitution on the indole nucleus occurred exclusively at the 3-position, and N-alkylation products have not been observed.

The Michael addition of indoles to alpha,beta-unsaturated ketones catalyzed by CeCl3.7H2O-NaI combination supported on silica gel.

Cerium (III) Chloride, a Novel Reagent for Nonaqueous Selective Conversion of Dioxolanes to Carbonyl Compounds

A nitrone-based approach to the enantioselective total synthesis of (-)-anisomycin

The synthetic potentialities of cerium(III) chloride are demonstrated by the synthesis of a nine-membered ring heterocycle component of Griseoviridin (3) in optically active form. The key step involves the stereospecific formation of the α-carbalkoxy alkenyl sulfide moiety using a combination system of cerium(III) chloride heptahydrate and sodium iodide.

Enrico Marcantoni

Papers

Chemo- and Diastereoselective Reduction of .beta.-Enamino Esters: A Convenient Synthesis of Both cis- and trans-.gamma.-Amino Alcohols and .beta.-Amino Esters

The Michael addition of indoles to alpha,beta-unsaturated ketones catalyzed by CeCl3.7H2O-NaI combination supported on silica gel.

Cerium (III) Chloride, a Novel Reagent for Nonaqueous Selective Conversion of Dioxolanes to Carbonyl Compounds

A nitrone-based approach to the enantioselective total synthesis of (-)-anisomycin

A novel route to the vinyl sulfide nine-membered macrocycle moiety of Griseoviridin.