Electrochemistry represents one of the most intimate ways of interacting with molecules. This review discusses advances in synthetic organic electrochemistry since 2000. Enabling methods and synthetic applications are analyzed alongside innate advantages as well as future challenges of electroorganic chemistry.

Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance

Molecular separation with organic solvent nanofiltration: a critical review.

Advances in the chemistry of tetrahydroquinolines.

Conventional methods for carrying out carbon–hydrogen functionalization and carbon–nitrogen bond formation are typically conducted at elevated temperatures, and rely on expensive catalysts as well as the use of stoichiometric, and perhaps toxic, oxidants. In this regard, electrochemical synthesis has recently been recognized as a sustainable and scalable strategy for the construction of challenging carbon–carbon and carbon–heteroatom bonds. Here, electrosynthesis has proven to be an environmentally benign, highly effective and versatile platform for achieving a wide range of nonclassical bond disconnections via generation of radical intermediates under mild reaction conditions. This review provides an overview on the use of anodic electrochemical methods for expediting the development of carbon–hydrogen functionalization and carbon–nitrogen bond formation strategies. Emphasis is placed on methodology development and mechanistic insight and aims to provide inspiration for future synthetic applications in the field of electrosynthesis.

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Electrochemical strategies for C-H functionalization and C-N bond formation.

The different types of acceptorless alcohol dehydrogenation (AAD) reactions are discussed, followed by the catalysts and mechanisms involved. Special emphasis is put on the common appearance in AAD of pincer ligands, of noninnocent ligands, and of outer sphere mechanisms. Early work emphasized precious metals, mainly Ru and Ir, but interest in nonprecious metal AAD catalysis is growing. Alcohol–amine combinations are discussed to the extent that net oxidation occurs by loss of H2. These reactions are of potential synthetic interest because they can lead to N heterocycles such as pyrroles and pyridines. AAD also has green chemistry credentials in that an oxidation occurs without the need for an oxidizing agent and hence without the waste formation that would result from its use.

Homogeneous Transition Metal Catalysis of Acceptorless Dehydrogenative Alcohol Oxidation: Applications in Hydrogen Storage and to Heterocycle Synthesis

This article outlines the biological significance of one of the most important heterocycles, the pyrimidine. An attempt has been made to cover most of the physiologically as well as medicinally important compounds containing pyrimidine and its derivatives.

Biological and medicinal significance of pyrimidines

A review. The stereoselective formation of carbon-carbon double bonds is a longstanding topic in org. chem. Since the early 90s, catalytic olefin metathesis has emerged as a synthetic tool of choice for the creation of carbon-carbon double bonds, and its use is now widespread. However, except for the synthesis of small cycles, the reversible character of olefin metathesis usually results in the formation of the thermodn. E product, and more generally in mixts. of E and Z products. This issue has been addressed in different ways; these are reviewed herein. Synthetic protocols, which aim at the selective synthesis of Z olefins, for example, sequential alkyne metathesis/cis-hydrogenation, and the use of removable silyl groups, are summarized. Tailor-made molybdenum, tungsten and ruthenium catalysts, which allow for very high stereoselectivity, are also reviewed. The advances achieved with these methods and catalysts are illustrated by the synthesis of various natural products or their precursors. [on SciFinder(R)]

Z Selectivity: Recent Advances in one of the Current Major Challenges of Olefin Metathesis

The stereoselective convergent total syntheses of both enantiomers of the tetrahydroisoquinoline (THIQ) alkaloid crispine A are described. The THIQ precursors (−)-6 (90:10 dr) and (−)-11 (85:15 dr) were prepared from the alkylation–reduction sequence of a common α-amino nitrile (+)-4 derivative that has been conveniently prepared by anodic cyanation. Elaboration of the pyrrolidine ring of the title compound was cleanly achieved by two efficient ring closures methods involving (a) the displacement of a halogen atom and (b) the formation of a cyclic iminium cation to afford (−)-crispine A in 90% and 85% yields, respectively. A crystallization of enantioenriched (−)-crispine A (90:10 er) with 1 equiv of (−)-DBTA afforded the tartrate salt (−)-14 (≥98:2 dr) in 81% yield. The absolute S configuration of (−)-crispine A was simply deduced from examination of the X-ray data of tartrate salt (−)-14. Likewise, the natural (+)-crispine A was prepared in seven workup steps in an overall 30% yield, and reciprocal crys...

Electrochemical Synthesis and Chemistry of Chiral 1-Cyanotetrahydroisoquinolines. An Approach to the Asymmetric Syntheses of the Alkaloid (−)-Crispine A and Its Natural (+)-Antipode

Saurabh Shahane

Papers

Biological and medicinal significance of pyrimidines

Z Selectivity: Recent Advances in one of the Current Major Challenges of Olefin Metathesis

Electrochemical Synthesis and Chemistry of Chiral 1-Cyanotetrahydroisoquinolines. An Approach to the Asymmetric Syntheses of the Alkaloid (−)-Crispine A and Its Natural (+)-Antipode

Synthesis of Alkaloids of Galipea officinalis by Alkylation of an α‐Amino Nitrile

Acceptorless ruthenium catalyzed dehydrogenation of alcohols to ketones and esters