Dehydrohalogenative polycondensation of 2-bromo-3-hexylthiophene was successful with Herrmann's catalyst and tris(2-dimethylaminophenyl)phosphine as precursors, giving head-to-tail poly(3-hexylthiophene) (HT-P3HT) high molecular weight (Mn = 30 600, Mw/Mn 1.60) regioregularity (98%) in almost quantitative yield (99%).

Asymmetric alkynylation of both aromatic and aliphatic aldehydes using catalytic amounts In(III)/BINOL is described. Dual activation substrates due to the "bifunctional character" indium(III) catalyst enables a broad range substrate generality with high enantioselectivity (83 >99% ee).

Borylzincate was generated in situ from dialkylzinc, diboron, and metal alkoxide. Model DFT calculations showed that although the formation of borylzincate is kinetically favorable, it thermodynamically unfavorable. Therefore, we designed a successive reaction sequence would provide compensating energy gain. This enabled Zn-catalyzed borylation aryl halides borylzincation benzynes terminal alkyne diborons without need for any cocatalyst.

We present the first trans-selective diborylation reaction of alkynes. By means theoretical calculation-assisted analysis, we designed a pseudo-intramolecular diboron, propargyl alcohol, and base to facilitate B–B bond activation C–B formation with high efficiency. This approach provides synthetically versatile densely functionalized 4-borylated 1,2-oxaborol-2(5H)-oles (vinyldiboronates) in straightforward manner. Detailed computational analysis showed that directing alkoxide functionality...

Deprotonative directed ortho cupration of aromatic/heteroaromatic C–H bond and subsequent oxidation with t-BuOOH furnished functionalized phenols in high yields regio- chemoselectivity. DFT calculations revealed that this hydroxylation reaction proceeds via a copper (I → III I) redox mechanism. Application to aromatic amination using BnONH2 efficiently afforded the corresponding primary anilines. These reactions show broad scope good functional group compatibility. Catalytic versions these...

The enantioselective total synthesis of (−)-strychnine was accomplished through the use highly practical catalytic asymmetric Michael reaction (0.1 mol % (R)-ALB, more than kilogram scale, without chromatography, 91% yield and >99% ee) as well a tandem cyclization that simultaneously constructed B- D-rings (>77% yield). Moreover, newly developed conditions for thionium ion cyclization, NaBH3CN reduction imine moiety in presence Lewis acid to prevent ring opening reaction, chemoselective...

[reaction: see text] A new entry in catalytic alkynylation of carbonyl compounds was developed which dual activation both soft nucleophiles (terminal alkynes) and hard electrophiles (aldehydes ketones) is achieved using an indium(III) catalyst. Preliminary mechanistic studies situ IR NMR spectroscopic analysis are also discussed.

An etheric Negishi coupling: The first cross-coupling reaction between aryl alkyl ethers and dianion-type zincate reagents to afford biaryl compounds through selective cleavage of the C(sp2)O bond was developed. Dianion-type zincates showed excellent reactivity toward aromatic under mild conditions, with good functional group compatibility (see scheme).

Abstract A method for the nucleophilic amination of methoxy arenes was established by using sodium hydride (NaH) in presence lithium iodide (LiI). This offers an efficient route to benzannulated nitrogen heterocycles. Mechanistic studies showed that reaction proceeds through unusual concerted aromatic substitution.

We describe the development of a general catalytic asymmetric Michael reaction acyclic beta-keto esters to cyclic enones, in which induction occurs at beta-position acceptors. Among various catalyst systems examined, newly developed La-NR-linked-BINOL complexes (R = H or Me) afforded best results terms reactivity and selectivity. In general, NMe ligand 2 was suitable for combination small enones esters, NH 1 bulkier substrates (steric tuning catalyst). Using La-NMe-linked-BINOL complex,...

Enzyme-catalyzed [4+2] cycloaddition has been proposed to be a key transformation process in various natural product biosynthetic pathways. Recently Fsa2 was found involved stereospecific trans-decalin formation during the biosynthesis of equisetin, potent HIV-1 integrase inhibitor. To understand mechanisms by which fsa2 determines stereochemistry reaction products, we sought an homologue that is pathway enantiomerically opposite analogue, and phm7, phomasetin. A decalin skeleton with...

New protocols for controlled reduction of carboxamides to either alcohols or amines were established using a combination sodium hydride (NaH) and zinc halides (ZnX2 ). Use different halide on ZnX2 dictates the selectivity, wherein NaH-ZnI2 system delivers NaH-ZnCl2 gives amines. Extensive mechanistic studies by experimental theoretical approaches imply that polymeric (ZnH2 )∞ is responsible alcohol formation, whereas dimeric chloride (H-Zn-Cl)2 key species production

π-Conjugated polymers are widely used in optoelectronics for fabrication of organic photovoltaic devices, light-emitting diodes, field effect transistors, and so on. Here we describe the protocol polycondensation bifunctional aryl ethers or ammonium salts with aromatic dimetallic compounds through cleavage inert C-O/C-N bonds. This reaction proceeds smoothly presence commercially available Ni/Pd catalyst under mild conditions, affording corresponding π-conjugated high molecular weight. The...

The mechanism of our previously reported catalytic asymmetric bromocyclization reactions using 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP) monoxide was examined in detail by the means control experiments, NMR studies, X-ray structure analysis, and CryoSpray electrospray ionization mass spectrometry (ESI-MS) analysis. chiral BINAP transformed to a key catalyst precursor, proton-bridged bisphosphine oxide complex (POHOP·Br), presence N-bromosuccinimide (NBS) contaminating water....

Conjugation between σ- and π-aromatic moieties in 1-C-arylated monocarba-closo-dodecaborate anion derivatives 2 has been identified by means of kinetic experimental studies combined with theoretical calculations. We found that the reaction rate iodination at 12-B vertex carborane cage was affected distal substituents on benzene ring connected antipodal carbon vertex. Hammett Yukawa–Tsuno plots indicated substantial resonance effects are involved. Density functional theory calculations...

Experimental and spectroscopic studies revealed unprecedented reactivity of a "naked" lithium cation with very weakly coordinating anions, including carborane anions. The superactivated has greatly enhanced Lewis acidic character mediates various organic reactions such as carbonyl-ene reaction, NBS-bromination unactivated aromatics, Friedel-Crafts alkylation, which are not promoted by conventional salts. Chemical robustness the counteranion also plays an important role in chemistry strongly...

The iodoform reaction has long been used as a qualitative test for acetyl and/or ethanol units in organic molecules. However, its synthetic applications are quite limited. Here, we describe tuned oxidative demethylation with I

A protocol for regio-controlled hydromagnesiation of 1,3-enynes was developed using magnesium hydride that is generated in situ by solvothermal treatment sodium (NaH) and iodide (MgI2 ) THF. The resulting allenylmagnesium species could be converted into tri- tetra-substituted allenes subsequent with various carbon- silicon-based electrophiles the aid CuCN as a catalyst.

The stereocontrolled total synthesis of (±)-halichonine B was achieved in 18 steps for the longest linear sequence. This features stereoselective construction a trans-fused dehydrodecalin framework containing three consecutive stereocenters through sequential intramolecular conjugate additions. Additionally, strategic use nitrobenzenesulfonamides enabled efficient installation branched diamine moiety.

Post-translational modifications (PTMs) of proteins play a crucial role in dynamically regulating cellular biological processes. Chemical catalysts have emerged as versatile tools for probing and modulating PTMs. A hydroxamic acid-thiol conjugated (HXA-SH) catalyst, mBnA, functionally mimics acetyltransferases by uniquely activating endogenous acetyl-coenzyme (Ac-CoA) to promote regioselective lysine acetylation targeted living cells. However, its in-cell activity has remained insufficient...

Indium(III)-catalyzed asymmetric alkynylation of aryl, heteroaryl, alkyl and alkenyl aldehydes with 2-methyl-3-butyn-2-ol as an ethyne equivalent donor was realized, products were obtained in moderate to good yields (up 97%) high enantioselectivities 99% ee) using 2-10 mol% catalyst.

The balance between the ring-walking process and oxidative-addition state are key determinants of catalyst mobility in catalyst-transfer condensation polymerization.

New couple: A cross-coupling reaction at the carbon vertex of a monocarba-closo-dodecaborate has been developed to allow efficient introduction various aryl groups and other sp2/sp-hybridized centers. copper(I) complex facilitated coupling process with wide range electrophiles room temperature. The was used prepare series C-arylated carborane anion derivatives (see picture; B green, C blue), some which showed androgen-receptor binding activity also mesogenic properties.