allylation performed in aqueous media, an efficient synthesis of highly functionalized lactones was realized in good yields (64− 77%, Scheme 29). 238 However, the chirality installed during the first step almost had no influence on the second step, thus resulting in poor diastereoselectivity in the subsequent allylation reaction (1:1−2:1 dr).In situ formation of aldehyde from the oxidation of alcohol followed by one-pot indium-mediated allylation also provides an alternative method for the synthesis of homoallylic alcohol. Recently, Yadav and co-workers developed such a one-pot sequence by using chloramines-T (sodium salt of Nchlorotosylamide) as oxidant in the presence of a catalytic amount of FeCl 3 in CH 2 Cl 2 , giving rise to homoallylic alcohols in good to excellent yields (Scheme 30). 239 It is noteworthy that the generated byproduct of TsNH 2 (from the reduction of chloramines-T) may react with the in situ-formed aldehydes to give intermediates of N-tosylimines in the presence of 4 Å molecular sieve under refluxing; the thus-formed N-tosylimines subsequently underwent one-pot indium-mediated allylation to produce homoallylic amines in 60−80% yields. Later, a similar one-pot, two-step sequence for the synthesis of homoallylic alcohols via a galactose oxidase-mediated chemo-enzymatic oxidation of benzyl and cinnamyl alcohols to the corresponding Scheme 23 Scheme 24 Scheme 25 Scheme 26 Scheme 27 Scheme 28 Scheme 29 Scheme 30 Chemical Reviews Review dx.

As the "chemical chameleon", sulfonyl-containing compounds and their variants have been merged with various types of reactions for the efficient construction of diverse molecular architectures by taking advantage of their incredible reactive flexibility. Currently, their involvement in radical transformations, in which the sulfonyl group typically acts as a leaving group via selective C−S, N−S, O−S, S−S, and Se−S bond cleavage/ functionalization, has facilitated new bond formation strategies which are complementary to classical two-electron cross-couplings via organometallic or ionic intermediates. Considering the great influence and synthetic potential of these novel avenues, we summarize recent advances in this rapidly expanding area by discussing the reaction designs, substrate scopes, mechanistic studies, and their limitations, outlining the state-of-the-art processes involved in radical-mediated desulfonylation and related transformations. With a specific emphasis on their synthetic applications, we believe this review will be useful for medicinal and synthetic organic chemists who are interested in radical chemistry and radical-mediated desulfonylation in particular. CONTENTS

Chemoselective functionalizations of intrinsically less reactive C(sp 3 )−H bonds of alkyl nitriles are of particular interest to the chemical community because these strategies provide opportunities for the introduction of important cyanoalkyl groups onto target frameworks in a step-economical fashion. In recent years, the introduction of nitrile-containing alkyl radicals in tandem radical additions and oxidative couplings has inarguably brought chemists a new radical reaction platform for the diverse synthesis of natural products and pharmaceuticals. Compared with the wide applications of various C-centered radicals adjacent to a heteroatom, however, nitrile-containing alkyl radicals remain largely unexplored. New methods for C(sp 3 )−H bond oxidative functionalization of alkyl nitriles and new mechanistic manifolds would result in the development of a broad range of novel reactions. Therefore, this review will give an overview of various types of radical cyanoalkylation using the key alkyl nitrile reactants, which lie beyond traditional coupling chemistry.

An efficient one-pot synthesis of 4,5,6-triaryl-3,4-dihydropyrimidin-2(1H)-ones via a three-component Biginelli-type condensation of aldehyde, 2-phenylacetophenone, and urea/thiourea in the presence of a catalytic amount of t-BuOK (20 mol %) is described. The reactions proceeded efficiently at 70 degrees C to afford the desired products in moderate to good yields. Detailed mechanistic study shows that the Biginelli-type reaction using urea and thiourea proceeds through two totally different pathways. Enone 5 and bis-urea 8 were highly suggested as respective reaction intermediates for reactions involving thiourea and urea as substrates.

Women with endometriosis (EMs) have unexplained infertility. The recently identified telocytes (TCs) might participate in the maintenance of structural and functional integrity of oviduct tissue, but so far the involvement of TCs in EMs-affected oviduct tissue and potential impact on fertility capacity remain unknown. By an integrated technique of haematoxylin and eosin staining, in situ immunohistochemistry and double-labelled immunofluorescence staining and electron microscopy approach, TCs were studied in the autotransplantation Sprague–Dawley rat model of EMs-affected oviduct tissue and in sham control, respectively, together with determination of iNOS, COX-2, LPO and estradiol. TCs were found in perivascular connective tissue and smooth muscle bundles in sham oviduct, with typical ultrastructural features (a slender piriform/spindle/triangular cell body, and one or more extremely long prolongations, emerged from cell bodies and extend to various directions), and specific immunophenotype of CD34-positive/vimentin-positive/c-kit-negative. However, in EMs-affected oviduct tissue (grade III), extensive ultrastructural damage (degeneration, discontinue, dissolution and destruction), significant decrease or loss of TCs and interstitial fibrosis were observed, together with elevated level of iNOS, COX-2, LPO and estradiol, thus suggestive of inflammation and ischaemia-induced TCs damage. Based on TCs distribution and intercellular connections, we proposed that such damage might be involved in structural and functional abnormalities of oviduct, such as attenuated intercellular signalling and oviduct contractility, impaired immunoregulation and stem cell-mediated tissue repair, 3-D interstitial architectural derangement and tissue fibrosis. Therefore, TCs damage might provide a new explanation and potential target for EMs-induced tubal damage and fertility disorders.

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Transition metal-catalyzed cross-coupling reactions using organoindium reagents have witnessed rapid and comprehensive development in the past two decades. In comparison with many other organometallic reagents, the preparation of organoindium reagents and the subsequent transition metal-catalyzed cross-coupling reactions with various electrophiles showed a wider tolerance to important functional groups and protic solvents. In addition, in many cases, cross-coupling reactions employing organoindium reagents exhibited remarkable chemo- and stereoselectivity. In this tutorial review, we summarize and highlight the most important developments in this rapidly advancing area, with special emphasis on their utilities in organic synthesis and materials science.

We previously reported frequent loss of microRNA-218 (miR-218) in cervical cancer, which was associated with tumor progression and poor prognosis. As microRNAs were found invovled in the regulation of radiosensitivity in various human cancers, we therefore aim to investigate the effects of miR-218 on radiosensitivity of cervical cancer in the present study. The clonogenic survival assay demonstrated that loss of miR-218 could predict radioresistance in the primary cervical cancer cells (R2=0.6516, P<0.001). In vitro, abundant miR-218 increased the radiosensitivity in cervical cancer cells (P<0.001 for HeLa, P=0.009 for SiHa, P=0.016 for C33A and P=0.01 for CaSki). Upregulation of miR-218 significantly enhanced the radiation-induced apoptosis, which was further enhanced by the combination of miR-218 overexpression and radiation In xenograft growth assay, combination of miR-218 overexpression and radiation notably induced cellular apoptosis and suppressed tumor growth. In conclusion, we demonstrated that miR-218 resensitized cervical cancer cells to radiation via promoting cellular apoptosis. Moreover, we proved that miR-218 as a potent predictor of radiosensitivity in cervical cancer, especially for those patients with loss of miR-218.