The Pd-benzothiazol-2-ylidene complex I was found to be a chemoselective catalyst for the Tsuji-Trost allylation of active methylene compounds carried out under neutral conditions and using carbonates as allylating agents. The proposed protocol consists in a simplified procedure adopting an in situ prepared catalyst from Pd2dba3 and 3-methylbenzothiazolium salt V as precursors. A comparison of ...

The first example of a biocatalytic strategy for the synthesis of thioethers via an intermolecular carbene S–H insertion reaction is reported. Engineered variants of sperm whale myoglobin were found to efficiently catalyze this C–S bond forming transformation across a diverse set of aryl and alkyl mercaptan substrates and a-diazoester carbene donors, providing high conversions (60–99%) and high...

The application of N-heterocyclic carbene complexes as active sites in materials other than catalysis has been remarkably scarce. Inspired by the - often misleading - 'carbene' label, which implies a substantial degree of M = C pi bonding, we have been interested in evaluating the potential of N-heterocyclic carbene complexes as building blocks for constructing electronically active materials. ...

The mol-ecular structure of the title compound, [WCl(2)(NO)(2)(C(21)H(24)N(2))(2)]·C(4)D(8)O, displays a distorted octa-hedral arrangement around the W atom with two trans 1,3-bis-(2,4,6-trimethyl-phen-yl)imidazol-2-yl-idene (IMes) carbene ligands in axial positions. The four equatorial positions are occupied by nitrosyl and chloride ligands, which are trans to each other. The C(carbene)-W-C(ca...

The cyclic alkyl(amino) carbene (cAAC) [:C{N-C6H3(2,6-IPr2)}(CMe2)2CH2] stabilized MeGeGeMe has been isolated in the molecular form with composition (cAAC)MeGe-GeMe(cAAC) (1) at room temperature. Compound 1 was synthesized from the reduction of MeGeCl3 using three equivalents of KC8 in the presence of one equivalent of cAAC. The corresponding silicon compound (cAAC)MeSi-SiMe(cAAC) (2) was also ...

Previous studies of the inter—relationships between isocyanide, imine, and carbene ligands on platinum(II), and of the stereochemistries of the latter two ligands will be briefly reviewed. Attempts to use these relationships to prepare platinum—olefin—carbene complexes have been unsuccessful but have led to an interesting ortho—metallated carbene derivative. The insertion of isocyanide into the...

Chemical modifications on histones and DNA/RNA constitute a fundamental mechanism for epigenetic regulation. These modifications often function as docking marks to recruit or stabilize cognate "reader" proteins. So far, a platform for quantitative and high-throughput profiling of the epigenetic interactome is urgently needed but still lacking. Here, we report a 3D-carbene chip-based surface pla...

The influence of spectator ligand bite angle and the twist angle of the carbene on the reductive elimination of N-heterocyclic carbenes (NHCs) from palladium bis-phosphine complexes has been investigated using density functional theory. The spectator bite angle was found to have a significant influence on both the activation energy (E(act)) and the enthalpy of reaction. Widening of the bite ang...

Following the recent discovery that heme proteins can catalyze the cyclopropanation of styrenyl olefins with high efficiency and selectivity, interest in developing new enzymes for a variety of non-natural carbene transfer reactions has burgeoned. The fact that diazo compounds and other carbene precursors are known mechanism-based inhibitors of P450s, however, led us to investigate if they also...

The nature of the active species which lead to the formation of the initiator carbene in photocatalytic metathesis reaction was investigated. The solid phase produced during irradiation was found to involve the active species while the soluble species showed no catalytic activity. The structure of the active solid was analyzed by ESCA, FT IR, NMR and chemical analysis methods and defined as a t...