The broad potential synthetic usefulness of phosphine-promoted reactions has stimulated many recent investigations on enantioselective variants known this family, as well the search for new, specifically designed, chiral phosphorus catalysts. This short overview summarizes state art in field and highlights most significant achievements, with special emphasis our work.

Planar chiral phosphines displaying a new ferrocenophane scaffold have been prepared via stereoselective approach. The P-cyclohexyl substituted phosphine affords high levels of asymmetric induction in the organocatalytic [3 + 2] annulation reaction between allenes and electron-poor olefins.

Electrophilic and nucleophilic terminal-phosphinidene complexes are compared in terms of electronic structures reactivities. Various precursors the unstable electrophilic species [R−P−M] (M=Cr, Mo, W(CO)5 Fe(CO)4) discussed. The addition reactions phosphinidene with Lewis bases, insertion into O−H, N−H, activated C−H bonds, cycloaddition double triple bonds described, as well some rearrangements autocondensations. applications to synthesis new organophosphorus molecules discussed techniques...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTGeneration and trapping of terminal phosphinidene complexes. Synthesis x-ray crystal structure stable phosphirene complexesAngela Marinetti, Francois Mathey, Jean Fischer, Andre MitschlerCite this: J. Am. Chem. Soc. 1982, 104, 16, 4484–4485Publication Date (Print):August 1, 1982Publication History Published online1 May 2002Published inissue 1 August...

Power of P: Phosphine-promoted [3+2] annulation reactions between electron-poor allenes and 3-arylidene indolin-2-ones afford a new organocatalytic strategy for the synthesis spirocyclic core oxindolic cyclopentanes (see scheme). Asymmetric variants these have been implemented by using chiral catalysts, giving very high levels asymmetric induction. Detailed facts importance to specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not copy-edited or...

Abstract This paper discloses the first uses of phosphahelicenes as chiral ligands in transition‐metal catalysis. Unlike all known helical phosphines used so far catalysis, phosphorus function is embedded structure itself. crucial structural feature originates unprecedented catalytic behaviors and efficiency. An appropriate design fine tuning allowed both high activity good enantiomeric excesses to be attained gold promoted cycloisomerizations N‐tethered 1,6‐enynes dien‐ynes.

This literature overview demonstrates that helically chiral ligands and organocatalysts have been largely neglected so far. However, a few recent studies on helical pyridine, the corresponding ammonium salts N-oxides highlighted significant potential of these compounds as for Michael type additions, aldehyde propargylations, epoxide openings, others. In addition, helicenes displaying fused phosphole ring at end their polyaromatic structures, used in enantioselective gold promoted...

N-Heterocyclic carbene (NHC) platinum complexes have been highlighted as a promising and original platform for building new cytotoxic drugs of the cisplatin series. Mixed NHC-amine PtII prepared via facile modular two step sequence leading to trans-configured square planar species. They characterized by spectroscopic methods X-ray diffraction studies. Their efficiency against both sensitive (CEM H460) resistant (A2780/DDP, CH1/DDP, SK-OV-3) cell lines has demonstrated in vitro experiments.

Abstract The first use of phosphahelicene in enantioselective organocatalysis is reported. New chiral phosphahelicenes have been prepared and enable highly [3+2] cyclization reactions between arylidene‐ or alkylidenemalononitriles γ‐substituted allenoates cyanoallenes. These afford cyclopentene derivatives both high yields diastereoselectivities, with enantiomeric excesses up to 97 %.

Triphenylphosphine promoted reactions between 3-arylideneoxindoles and δ-aryl-substituted penta-2,3-dienoates afford an unprecedented access to spirocyclic oxindoles with functionalized six-membered rings. In these new [4 + 2] cyclization processes, the allenoates operate as four-carbon synthons, thanks involvement of substituted δ-carbons. These give excellent control relative stereochemistry three stereogenic centers. The final product has been ascertained by X-ray diffraction studies.

Abstract During the last few years, synthetic methods based on phosphine organocatalysis have experienced extremely fast developments. This short overview is intended to demonstrate that these can afford suitable tools for constitution of either focused or diversity‐oriented‐synthesis (DOS) inspired libraries small molecules biological screening. It also reports selected examples where organocatalytic been used conveniently as key steps in formal total synthesis complex natural products....

Tethering a metal complex to its phosphate counterion via phosphine ligand enables new strategy in asymmetric counteranion-directed catalysis (ACDC). A straightforward, scalable synthetic route gives access the gold(I) of displaying chiral phosphoric acid function. The generates catalytically active species with an unprecedented intramolecular relationship between cationic Au(I) center and counterion. benefits tethering two functions catalyst are demonstrated here tandem...

Gold(I) complexes of a chiral phosphoric acid-functionalized phosphine the CPA-Phos series enable enantioselective multicomponent reactions between aldehydes, hydroxylamines and cyclic yne-enones, leading to 3,4-dihydro-1H-furo[3,4-d][1,2]oxazines. This represents rare example highly reaction in gold(I) catalysis. The proceed at low catalyst loading provide high yields, total diastereoselectivity, enantiomeric excesses up 99%. Silver-free conditions can be applied. method has very broad...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTThe carbene-like behavior of terminal phosphinidene complexes toward olefins. A new access to the phosphirane ringAngela Marinetti and Francois MatheyCite this: Organometallics 1984, 3, 456–461Publication Date (Print):March 1, 1984Publication History Published online1 May 2002Published inissue 1 March 1984https://pubs.acs.org/doi/10.1021/om00081a021https://doi.org/10.1021/om00081a021research-articleACS PublicationsRequest reuse permissionsArticle...

The reaction of dimethyl acetylenedicarboxylate with LM(CO)5 complexes (L = 1 -substituted-3,4-dimethyl-phosphole; M Cr, Mo, W) provides an easy access to stable 7-phosphanornadiene complexes, the X-ray crystal one which is reported; 31P resonance these species appears at very low field (ca. 200–260 p.p.m.) and mass spectral structural data suggest that they may be efficient generators for still unknown terminal phosphinidene complexes.

A new family of cyclometalated (N-heterocyclic carbene)-Pt(II) complexes bearing monodentate phosphines as ancillary ligands has been designed for use precatalysts in 1,6-enyne cycloisomerization reactions. Highly enantioselective skeletal rearrangements allylpropargyl-tosylamide derivatives have developed by using (S)-Ph-Binepine the chiral auxiliary. Enantiomeric excesses up to 97% obtained.

The planar chiral 2-phospha[3]ferrocenophane I has been shown to be the first efficient nucleophilic organocatalyst for enantioselective synthesis of cyclopentenylphosphonates, through [3+2] cyclizations between diethyl allenylphosphonate and alpha,beta-unsaturated ketones. same catalyst also applied highly allenic esters with dibenzylideneacetone analogous bis-enones, leading functionalised cyclopentenes either monocyclic or spirocyclic structures (ee 84-95 %). It that residual enone...

Abstract Enantiomerically pure thiahelicenes displaying a terminal phosphole unit and stereogenic phosphorus center have been prepared by oxidative photocyclization of diaryl‐olefin precursor. Starting from one these phosphathiahelicene oxides, the corresponding trivalent phosphine–Au I complex is obtained with complete diastereoselectivity. It affords new, excellent precatalyst for enantioselective cycloisomerization N‐tethered enynes (up to 96 % ee ).

Building helicenes: A photochemical cyclization approach affords helicenes in which the fused ring sequence ends with a phosphole unit (see scheme). The stereogenic phosphorus centers of substrates control screw sense helical chirality. terminal units undergo [2+2] annulations to give dimeric structures. Detailed facts importance specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not copy-edited or typeset. They made available submitted by...

A series of bimetallic [(NHC)PtX2]2(diamine) complexes have been prepared as a new chemotype for potential anticancer agents. These display an uncommon set structural features far they combine two bifunctional, trans-configured platinum centers. They cytotoxic activities in the micromolar range on many cancerous cell lines and do not cross-react with cisplatin A2780/DDP lines. bind slowly to double-stranded DNAs, giving monoadducts major products. Pathways cellular toxicity investigated both...

The phosphine-promoted [3 + 2] cyclizations between γ-substituted allenoates and arylideneoxindoles have been applied to the stereoselective synthesis of spiro(cyclopentene)oxindoles with trisubstituted cyclopentene units. It has demonstrated that PPh(3) operates a very efficient control relative stereochemistry three stereogenic centers final spiranic products. Focused experiments carried out then so as access carbocyclic analogues an important series anticancer agents inhibiting MDM2-p53...

Abstract N ‐Propargyl tryptamines bearing ‐substituents such as propargyl, allyl, alkyl or benzyl groups undergo regioselective gold‐catalyzed cyclizations to the corresponding spiroindolenines, while it was previously shown that ‐sulfonyl‐ ‐propargyl lead achiral azepino[4,5‐ b ]indoles. An asymmetric approach these spiroindolenines is disclosed using chiral gold complexes, leading enantiomeric ratios up 84/16. The could be late‐stage functionalized Huisgen cyclizations, palladium‐catalyzed...