ConspectusLactones and lactams are a well-known class of natural products can be used as building blocks in organic synthesis. In addition, they found many sources synthetic drugs have broad range biological or odorant properties. Chemists create these useful compounds through palladium catalysis, which is highly efficient tool for synthesis conveniently functional group tolerant. this Account, we describe our work over the past 15 years intramolecular Pd-catalyzed allylations where tethered...

Palladium represents one of the most exploited catalysts in organic synthesis, mainly applied versatile methods for formation C-C bonds, but also selective double bonds hydrogenation and oxidation processes, founding numerous industrial applications particular fine chemicals production. In last decade, use metallic nanoparticles catalysis has exploded (ca. 5,200 contributions period 2000-March 2010) specifically ca. 40% reported works corresponds to palladium applications. Despite this...

Palladium-catalyzed arylation of sulfenate anions generated from β-sulfinyl esters can take place under biphasic conditions. This hitherto unknown reaction provides a simple, mild, and efficient route to aryl sulfoxides in good yields. The development new pseudo-domino type I procedure involving sulfinylation followed by Mirozoki−Heck coupling is also described.

Arylation of various sulfenate anions generated from beta-sulfinyl esters by retro-Michael reaction in the presence palladium(0) and enantiopure ligands gave corresponding aryl sulfoxides enantio-enriched form. The Josiphos-type ligand (R)-(S)-PPF-t-Bu2 turned out to be best tested, allowing ee's up 83% a predictable sense.

Allylic sulfoxides, via [2,3]-sigmatropic rearrangement and oxidative addition of the resulting allylic sulfenate esters to Pd(0), are found be excellent precursors anions. This hitherto unknown reactivity is applied in a new Pd(0)-catalyzed domino sequence involving anion generation followed by arylation afford aryl sulfoxides.

In recent years, carbones have emerged as a new exciting class of carbon-based ligands. We report here series organometallic complexes demonstrating the versatility in coordination mode phosphine/sulfoxide carbone 1. Indeed, 1 is able to chelate both early and late transition metals, mono- or bidentate fashion depending on oxyphilic character metal center thanks presence sulfoxide moiety. All been fully characterized by X-ray diffraction analysis NMR spectroscopy (except hafnium complex...

The cyclodextrin-tetraphosphine hybrid coined α-Cytep allows turnover numbers up to 340 000 and frequencies 1 h−1 be reached in Suzuki–Miyaura reactions. These exceptional figures are clearly linked the outstanding longevity of reactive species induced by ligand illustrates rising potential cyclodextrins catalytic applications.

An allylic alkylation/ring-closing metathesis domino catalytic process, wherein a palladium and ruthenium catalyst are concomitantly present in the reaction mixture from outset of reaction, is developed. Evidence for Grubbs' catalysts activity alkylation also reported.

Palladium-catalyzed allylic alkylation of sulfenate anions, generated from beta-sulfinylesters by retro-Michael reaction, can take place under biphasic conditions. This new reaction provides a simple, mild, and efficient route to allyl sulfoxides in good yields.

Learning curve: Regioselective twofold deprotection of benzylated cyclodextrins with diisobutylaluminum hydride affords products that can behave as enantiomers. For example, they act ligands for enantioselective Pd0-catalyzed reactions and their complexes display opposite circular dichroism signals (see picture). They thus be seen being inherently chiral cycle surrogates. Detailed facts importance to specialist readers are published "Supporting Information". Such documents peer-reviewed, but...

Abstract The Pd‐catalyzed intramolecular allylic alkylation of unsaturated amides to give γ‐ and δ‐lactams has been studied in the presence chiral ligands. Ligand ( R )‐3,5‐ t Bu‐MeOBIPHEP (MeOBIPHEP=6,6’‐dimethoxybiphenyl‐2,2‐diyl)bis(diphenylphosphine)) afforded best results allowed cyclization reactions take place up 94:6 enantiomeric ratio. A model Pd–allyl complex prepared through NMR spectroscopic analysis, which provided insight into processes responsible for observed ratios. DFT...

The reactivity of amidinate (1a,b, 2a)- or NHC (5a,b)-stabilized germanium(II) compounds toward diiron nonacarbonyl has been investigated. These germylenes act as two-electron carbene-like ligands and lead to stable germylene iron complexes by exchange reaction a carbonyl ligand. Whereas the amidinato chloro complexes, bis(iron germylene) oxide was obtained from bis-amidinato germylene. reactions NHC-stabilized (5a,b) with Fe2(CO)9 were also explored, giving donor–acceptor germylenes. All...

A donor-stabilized silylene 4 featuring a Ni0 -based donating ligand was synthesized. Complex exhibits pyramidalized and nucleophilic SiII center shows peculiar behavior due to the cooperative reactivity of Si Ni centers. Calculations indicate that orientation Ni-ligands with respect moiety is crucial in determining role Ni-fragment (Lewis acid or Lewis base) towards silylene. Indeed, simple 90° rotation Si-Ni bond, reverses Ni, transforms classical silylene→Ni0 complex into an unprecedented...

Palladium-catalyzed intramolecular allylic alkylations of unsaturated EWG-activated amides can take place under phase-transfer conditions or in the presence a crown ether. These new reaction are milder and higher yielding than those previously reported. A rationalization for such an unexpected result is put forth validated by DFT-B3LYP calculations. The results suggest cyclization via counterion-free (E)-enolate TS.

Unsaturated malonyl esters underwent Pd-catalyzed intramolecular allylic alkylation to give 4-vinyl-substituted γ-lactones. In contrast the formerly studied cyclization of malonamides, this reaction could be achieved only with a substrate incorporating suitably positioned silicon moiety, which directs ionization toward desired η3-allylpalladium complex. The resulting 4-[dimethyl-(2-thienyl)silylvinyl]lactone subsequently engaged into Hiyama couplings various iodoarenes, corresponding...

Free to decide: Various 4-(alpha-styryl) gamma-lactams are synthesized in 61-88% yield by a phosphine-free palladium-catalyzed carbopalladation/allylic alkylation domino sequence (see scheme). The cyclization is totally regio- and diastereoselective favor of the 3,4-trans-disubstituted gamma-lactam. process successfully applied synthesis new aza analogue naturally occurring lignan (+)-oxo-parabenzlactone.

New catalytic systems based on in situ and preformed palladium nanoparticles ionic liquids (characterised by TEM) starting from acetate or dipalladiumtris(dibenzylideneacetone) have been applied the synthesis of 4-phenylbutan-2-one (II), a model compound for preparation fragrances. Imidazolium-based liquid containing methyl hydrogenophosphonate anion leads to an efficient Pd-catalyzed tandem coupling/reduction process, taking advantage multi-role this solvent (nanoparticles stabiliser, base,...

Abstract The synthesis and characterization of an E 2 CE bis‐sulfonyl aryl pincer ligand its efficiency for the stabilization compounds containing low‐valent Group 14 elements (Ge Sn) are reported. Complexation reaction these metallylenes with iron or tungsten complexes resulted in modulation oxygen atoms sulfonyl groups implicated elements, demonstrating original adjustable character O S‐C‐SO pincer.

An unusual series of germylenes and stannylenes stabilized by new tetradentate bis(amidine) ligands RNC(R′)N-linker-NC(R′)NR with a rigid naphthalene backbone has been prepared protonolysis reaction Lappert’s metallylenes [M(HMDS)2] (M = Ge or Sn). Germylenes were fully characterized NMR spectroscopy X-ray diffraction analysis. DFT calculations have performed to clarify the structural electronic properties associated ligands. Stannylene L1Sn shows reactivity through oxidation, oxidative...

The first pentafluorophenyl copper(I)-biarylsulfoxide complexes, existing as [Cu(C6F5)]4L2 both in the solution and solid state were prepared thoroughly characterized. Subsequently, photochemistry of complexes was explored, showing inherent well unprecedented photoreactivity biarylsulfoxide moiety within coordination sphere copper.

Abstract The synthesis of a silyliumylidene cation complex 2 stabilized by Ni 0 ‐based donating ligand is reported. Experimental and theoretical studies demonstrate that the highly electrophilic Si II center dative Ni→Si σ‐interaction π‐donations from amino‐ Ni‐moieties. Due to energetically close frontier orbitals localized on atoms, presents competitive reactivity at sites.

Abstract The efficiency of the deprotonated aryl bis‐sulfone [2,6‐{( p ‐tolyl)SO 2 } C 6 H 3 ] − as an O,C,O‐coordinating pincer‐type ligand was described. precursor synthesized using a straightforward palladium‐catalyzed cross‐coupling reaction. As result directed ortho metalation (DoM) through sulfonyl groups, selective lithiation group achieved and corresponding carbanion isolated its structure determined by single‐crystal X‐ray diffraction analysis. A heteroleptic tin(II) complex has...

Abstract The C 2 ‐symmetric compound 2,3,2,3‐tetrahydro‐2,2‐bi(benzo[ b ]thiophenyl) and three diastereomeric bis(oxide) derivatives can be synthesized in a few steps from benzo[ ]‐thiophene by oxidative homocoupling of ( R )‐2,3‐dihydro‐benzo[ ]thiophene 1‐oxide. This new family enantiopure bis(thioether) bis(sulfoxide) ligands forms stable chelating Pd II complexes. fused pentacyclic structure the complexes imparts rigid chiral environment around metal centre. (© Wiley‐VCH Verlag GmbH...