Trigger happy: A new cascade process initiated by an unprecedented [1,5]-hydride transfer/cyclization of ortho-aminophenyl alkynyl Fischer carbene complexes leads to the formation 1,2-dihydroquinolinyl and 5,6-dihydrophenantridine derivatives (see scheme).

A Cu/Pd-catalyzed allylboration of alkynes with allyl carbonates and bis(pinacolato)diboron to afford borylated skipped dienes is reported. Synergistic Cu Pd catalysis enables this protocol work for a wide array under mild conditions total regio- stereocontrol. This transformation features the catalytic generation β-borylalkenylcopper intermediates their use in Pd-catalyzed allylic substitution carbonates. The utility method highlighted by synthesis (Z,E)-α-homofarnesene (pheromone)...

A Cu(I)-phosphoramidite-based catalytic system that allows asymmetric allyl-allyl cross-coupling with high enantioselectivity is reported. This transformation tolerates a large variety of functionalized substrates. The versatility this new reaction illustrated in the synthesis Martinelline alkaloids chromene derivative core.

An efficient catalytic asymmetric synthesis of chiral γ-butenolides was developed based on the hetero-allylic alkylation (h-AAA) in combination with ring closing metathesis (RCM). The synthetic potential h-AAA-RCM protocol illustrated facile (−)-whiskey lactone, (−)-cognac (−)-nephrosteranic acid, and (−)-roccellaric acid.

Palladium-catalysed cross-coupling of secondary C(sp3) organometallic reagents has been a long-standing challenge in organic synthesis, due to the problems associated with undesired isomerisation or formation reduction products. Based on our recently developed catalytic C–C bond organolithium reagents, herein we present Pd-catalysed alkyllithium aryl and alkenyl bromides. The reaction proceeds at room temperature short timescales high selectivity yields. This methodology is also applicable...

An efficient and highly enantioselective copper-catalyzed allylic alkylation of disubstituted allyl halides with primary secondary organolithium reagents using phosphoramidite ligands is reported. The use trisubstituted bromides allows, for the first time, synthesis all-carbon quaternary stereogenic centers these reactive organometallic reagents. Detailed facts importance to specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not copy-edited or...

The unique reactivity of diaryliodonium salts with copper complexes has been applied to a variety synthetic organic transformations. These hypervalent iodine compounds have used for diverse copper-catalyzed cross-coupling reactions including C–H functionalizations, enantioselective C–C bond formation, cascade and different heteroatom arylation processes. This review provides summary recent developments on this topic discusses both the utility mechanisms these 1 Introduction 2 Historical...

A catalytic method for the direct cross-coupling of alkenyllithium reagents with aryl and alkenyl halides is described. The use a catalyst comprising Pd2(dba)3/XPhos allows stereoselective preparation wide variety substituted alkenes in high yields under mild conditions. In addition (1-ethoxyvinyl)lithium can be efficiently converted into vinyl ethers which, after hydrolysis, give readily access to corresponding methyl ketones one pot procedure.

Copper-catalysis allows the direct oxygen-arylation of dialkyl phosphonates with diaryliodonium salts. This novel methodology proceeds a wide range and phosphoramidates under mild conditions gives straightforward access to valuable mixed alkyl aryl in very good yields near perfect selectivity.

The synthesis of new cationic alkenyl Fischer-type gold(I) complexes through a carbene transfer reaction chromium and tungsten Fischer with LAuICl in the presence AgSbF6 is reported. stability resulting highly depends on nature ligand (L). We have used unstable for developing some catalytic reactions complexes.

A highly efficient method is reported for the asymmetric ring opening of oxabicyclic alkenes with organolithium reagents. Using a copper/chiral phosphoramidite complex together Lewis acid (BF(3)·OEt(2)), full selectivity anti isomer and excellent enantioselectivities were obtained opened products.

For the first time iridium catalysis has been used for synthesis of chiral tetrahydroisoquinolines with excellent yields and high enantioselectivities (see scheme; cod=1,5-cyclooctadiene, DBU=1,8-diazabicyclo[5.4.0]undec-7-ene). These products are important building blocks biologically active compounds, in particular alkaloids.

Palladium-catalyzed direct cross-coupling of aryl chlorides with a wide range (hetero)aryl lithium compounds is reported. The use Pd-PEPPSI-IPent or Pd2(dba)3/XPhos as the catalyst allows for preparation biaryl and heterobiaryl in high yields under mild conditions (room temperature to 40 °C) short reaction times.

Resolving the issue: A near-perfect Pd-catalyzed kinetic resolution of 1,3-disubstituted unsymmetrical allylic acetates uses silyl enol ethers as nucleophiles to access important 3-substituted-furanone scaffold (see scheme; DACH=diaminocyclohexyl, dba=dibenzylideneacetone). The reaction proceeds under mild conditions and provides desired products with excellent chemo-, regio-, enantioselectivity. Detailed facts importance specialist readers are published "Supporting Information". Such...

Elegant like a butterfly, stings lithium reagent: Mono- and di-ortho-substituted aryllithium reagents were coupled through palladium catalysis with hindered aryl bromides to form highly congested tri- tetra-ortho-substituted biaryls. The reaction allows the use of easily accessible ortho-functionalized compounds. high reactivity organolithium facilitates fast process under ambient conditions. As service our authors readers, this journal provides supporting information supplied by authors....

A highly regio- and enantioselective copper catalysed direct conjugate addition of Grignard reagents to chromones has been developed taking advantage the reduced reactivity resulting magnesium enolates. This methodology tolerates a broad scope alkyl Grignards including secondary as well functionalised chromones.

A palladium-catalysed cross-coupling of organolithium reagents with aryl and vinyl triflates is presented. The reaction proceeds at 50 or 70 °C short times, the corresponding products are obtained moderate to high yields, a variety alkyl (hetero)aryl lithium reagents.

Abstract An efficient method to access diversely substituted borylated dendralenes from simple and readily available materials is reported. This based on a multicomponent copper‐catalyzed allylboration of alkynes with diboron 1,4‐dibromo‐2‐butene which provides bromo‐ boron‐substituted skipped dienes remarkable chemo‐, stereo‐, regioselectivity. These products can be easily transformed into dendralenic organoboronates, display an extremely versatile reactivity as demonstrated by novel...

A catalytic asymmetric reaction between allenes, bis(pinacolato)diboron, and allylic gem-dichlorides is reported. The method involves the coupling of a catalytically generated allyl copper species with gem-dichloride provides chiral internal 1,5-dienes featuring (Z)-configured alkenyl boronate chloride units high levels chemo-, regio-, enantio-, diastereoselectivity. synthetic utility products demonstrated synthesis range optically active compounds. DFT calculations reveal key noncovalent...

Allylic gem-dichlorides undergo regio- and enanantioselective (er up to 99:1) copper-catalyzed allylic alkylation with Grignard reagents affording chiral Z-vinyl chlorides. This highly versatile class of synthons can be subjected Suzuki cross coupling optically active Z-alkenes 1,3-cis,trans dienes.

A highly efficient method for the enantioselective synthesis of 1,4-dienes (skipped dienes) with a methyl-substituted central stereogenic carbon using copper-catalysed asymmetric allylic alkylation diene bromides was developed. Excellent regio- and enantioselectivity (up to 97 : 3 SN2'/SN2 ratio 99% ee) were achieved broad substrate scope.