Read synthesis of chiral heterocyclic phosphines for application in asymmetric catalysis, cheminform on deepdyve, the largest online rental service for scholarly research with thousands of academic publications available at your fingertips. Synthesis and applications of pchirogenic and axially chiral. In general, bidentate phosphine ligands have been found to give excellent control in a number of catalytic asymmetric reactions. The asymmetric phosphinecatalyzed synthesis of pyrrolines has been challenging due to a. Design and synthesis of phosphine ligands for pallaiumcatalyzed coupling reactions by william scott brown a dissertation submitted in partial fulfillment of the requirements. Bidentate phosphine ligands for asymmetric synthesis quinoxp. The presence of an asymmetric carbon center is one of several structural features that induce chirality in organic and inorganic molecules. Catalytic enantioselective synthesis of quaternary 3,3. Chiral quest phosphine ligands in chemical synthesis sigma. Synthesis and applications of pchirogenic and axially. Andersson department of chemical and biological engineering organic chemistry chalmers university of technology abstract this thesis deals with the enantioselective synthesis of chiral mixed phosphorousnitrogen. Chiral quest phosphine ligands in chemical synthesis. Chiral phosphines are essential ligands for enantioselective metalcatalyzed reactions.
Design and synthesis of phosphine coupling reactions by. Synthesis and application of chiral monodentate phosphines. Herein, we present a direct pdxiaophoscatalyzed crosscoupling reaction of easily accessible secondary phosphine oxides and aryl bromides, which provides rapid access to p chiral phosphine oxides. Like nr 3, phosphines have a lone pair on the central atom that can be donated to a metal.
Asymmetric synthesis of chiral phosphines and arsines promoted by organometallic complexes liu fengli b. Design and synthesis of phosphine ligands for pallaiumcatalyzed coupling reactions by william scott brown a dissertation submitted in partial fulfillment of the requirements for the doctor of philosophy in the department of chemistry in the graduate school of the university of alabama tuscaloosa, alabama 2009. Recent advances in the application of chiral phosphine. In designing new phosphines there are a number of design features that need be. Enantioselective cucatalyzed arylation of secondary. Advanced studies on the synthesis of organophosphorus compounds. Furthermore, because the energy barrier to umbrella flipping of phosphines is quite high, chiralatphosphorus ligands can be isolated in enantioenriched form and introduced to metal centers, bringing asymmetry just about as close to the metal as it can get in chiral complexes. Pchiral phosphines are organophosphorus compounds of the formula prr.
P,nligands and organocatalysts have shown promise for further investigation. A versatile and efficient pdoac 2 1,1bisdiisopropylphosphinoferrocenecatalyzed crosscoupling of thiols with aryl halides was developed. Kwon chiral phosphines chiral catalysts, ligands, and. We demonstrate that allenes, chiral 1,2dienes, appended with basic functionality can serve as ligands for transition metals. Optically active phosphines which have a chiral center at phosphorus and can coordinate to transition metals. Synthesis and structures of allenecontaining ligands figure 1. Solution and solidstate structural analysis reveals that one olefin of the allene can.
Phosphorus nmr is a technique that just works thanks, nature. Synthesis of new chiral phosphines for asymmetric catalysis kagan. Although pstereogenic phosphines have been known as effective ligands for enantioselective catalysis for over 40 years, they are less frequently. These structurally different chiral phosphines can be selected to catalyze. The synthesis of novel 3 and 17diphenylphosphinoandrostane derivatives via homogeneous catalytic pc coupling is described. Sep 04, 2014 at present, the synthesis of new chiral phosphines designed specifically for nucleophilic organocatalysis remains a significant challenge. Synthesis of new chiral monodentate phosphines and their.
Functionalized chiral diazaphospholanes ligate to a variety of transition metals, yielding chiral, catalytically active, metal complexes. Chiral quest phosphine ligands one of the most efficient methods for constructing chiral compounds is asymmetric hydrogenation. School of physical and mathematical sciences a thesis submitted to the nanyang technological university in fulfillment of the requirement for. Synthesis of chiral primary amines and l actams 162 9. According to the nmr investigation of the ptcl2p2type complexes, the steroidal phosphines are transcoordinated with respect to the ptcentre exclusively. Synthesis of chiral phosphine oxides and phosphines via michaelis. Palladiumcatalyzed asymmetric addition of diarylphosphines. Syntheses and application of new chiral phosphines as. A novel method for the synthesis of chiral sulfonated phosphines. Chiral allenecontaining phosphines in asymmetric catalysis. Bph 4, where the phosphines pr2 have varying substituents. Advanced studies on the synthesis of organophosphorus. A straightforward synthesis of pchiral polycyclic phosphines by an asymmetric dielsalder reaction of 1alkyl1,2 diphospholes and 5r lmenthyloxy 25h furanone moxf is presented. According to the nmr investigation of the ptcl 2 p 2type complexes, the steroidal phosphines are trawscoordinated with respect to the ptcentre exclusively.
Synthesis of novel chiral quaternary phosphonium fluorides. These chiral ligands are typically divided into three design archetypes. The products were characterized by 1h and 31p nmr measurements. Synthesis of chiral heterocyclic phosphines for application. The new methods developed will be applied to the synthesis of important molecules. Pstereogenic compounds brandon rosen 29 march 2014. An easy demethylation of oanisyl phosphines provides a convenient access to a series of new chiral phosphinephosphites.
These include chiral phosphines, which are widely used in chemical industry but difficult and expensive to produce, novel catalysts and biocompatible polyester materials. Using phosphine aldehydes to generate new transition metal. Asymmetric catalytic performance is determined not only by the metal center but also by the chiral ligand selected. A general synthesis of chiral 4,5dihydro3hdinaphthophosphepines 1ag is described. The development of transitionmetalcatalyzed methods for the synthesis of p chiral phosphine derivatives poses a considerable challenge. Applicable to asymmetric hydrogenation under mild conditions applications. Previous work has established that amino acid derivatization of the carboxyl groups of r,r n,n.
Useful for asymmetric synthesis quinoxp advantages. For these reasons, effective chiral catalysts for nucleophilic phosphine catalysis are scarce, seriously limiting the development of asymmetric variants. Sep 30, 2016 classical methods for the synthesis of pstereogenic phosphines usually rely on auxiliarybased or resolution processes. The screening of these derivatives as ligands in rhodiumcatalyzed asymmetric hydrogenation of dimethyl itaconate has shown a. Cyclic chiral phosphines based on phospholane ring skeletons. All these phosphines behave presumably as bidentate ligands. At present, the synthesis of new chiral phosphines designed specifically for nucleophilic organocatalysis remains a significant challenge. Synthesis of new chiral phosphine ligands and their. Accelerated and enantioselective synthesis of a library of. Synthesis and applications of pchirogenic and axially chiral p,n phosphines as ligands and organocatalysts. Most of the chiral phosphines commonly used today display planar or point chirality where the asymmetric feature is presented in the carbon framework of the ligand. A chiral moleculeion is nonsuperposable on its mirror image. Enantioselective synthesis of pchiral tertiary phosphine. They are a subset of chiral phosphines, a broader class of compounds where the stereogenic center can reside at sites other than phosphorus.
Synthesis of pchiral phosphine ligands and their applications in. Aryl bromides and chlorides can be coupled to aliphatic and aromatic thiols the widest substrate scope of any reported to date. Accelerated and enantioselective synthesis of a library of p. Apr, 2004 functionalized chiral diazaphospholanes ligate to a variety of transition metals, yielding chiral, catalytically active, metal complexes. Enantioselective synthesis of planarchiral phosphines. First applications of 1ag in the rhodiumcatalyzed asymmetric hydrogenation of unsaturated carboxylic acid derivatives demonstrate the usefulness of our ligands. Chiral aminophosphines derived from hydroxyproline and. In the early exploration stage of asymmetric nucleophilic phosphine organocatalysis, chiral phosphines that had originally been designed as ligands for metalcatalyzed reactions were selected and examined. Kazumasa kanda, shoya oshima, tsubasa shizuno, risa hamanaka, miku fukai, takanori shibata. The synthesis of new chiral phosphines is of major importance for organic synthesis. Here we report cucatalyzed enantioselective arylation of secondary phosphine oxides with diaryliodonium salts for the synthesis of tertiary phosphine oxides with high enantiomeric excess. These compounds play a pivotal role as ligands and organocatalysts, respectively, in asymmetric reactions. Asymmetric synthesis of chiral phosphines and arsines.
Enantioselective acylations catalyzed by chiral phosphines. Synthesis of phosphines having chiral organic groups. Cyclic chiral phosphines based on spirocyclic skeletons. A robust synthetic route from lhydroxyproline lhyp to phosphines has established an expandable library of six chiral aminophosphines, which were. Airstable chiral primary phosphines part i synthesis. Catalytic asymmetric hydrogenations are among the most widely used industrial catalytic processes, due to their high turnover rates, efficiency and atom economy, and inexpensive material costs.
Synthesis of new chiral monodentate phosphines and their use. The resulting ligands represent a new class of monodentate chiral phosphines. The new process is demonstrated on a wide range of substrates and leads to products that are wellestablished. Asymmetric catalytic synthesis of pstereogenic phosphines. These compounds play a pivotal role as ligands and. The reaction proceeds efficiently with a wide array of. In addition, they may also be used as nucleophilic chiral catalysts for the synthesis of other chiral molecules. Catalytic synthesis of nonracemic pchiral phosphine derivatives remains a significant challenge.
Interconversions between pchiral molecules horner, tet. We describe an allenecontaining bisphosphine that, when coordinated to rhi, promotes the asymmetric addition of arylboronic acids to. Preparation of iridium complexes 46ag and 47ag 108 6. Solidphase synthesis of chiral 3,4diazaphospholanes and.
School of physical and mathematical sciences a thesis submitted to the nanyang technological university in fulfillment of the requirement for the degree of doctor of philosophy in chemistry 2010. Using phosphine aldehydes to generate new metal complexes and the synthesis of chiral nhcamino ligands kanghee park master of science. Sliding in an atmosphere of benzyl chloride promoted adsorption of chlorine to the iron surface. This work demonstrates, on a small scale, a synthetic strategy for making resolved chiral phosphines that are rich in functional groups, their combinatorial elaboration by solidphase synthesis, and their application to enantioselective asymmetric allylic. Enantioselectivities up to 95% ee for the hydrogenation of methyl. However, access to chiral phosphorus ligands is limited due to their challenging synthesis. Novel substituted diphenyl tertiary phosphines of a pyrrolidine carboxylic acid derivative and their use as catalysts in the enantioselective hydrogenation of. Synthesis and application of chiral monodentate phosphines in. Chiral phosphines play significant roles in asymmetric catalysis. Chiral aminophosphines derived from hydroxyproline and their. When chiral paryl phosphines were applied due to the chirality on the phosphorus, a mixture of epimers were formed which may cause varying enantioselectivities in consecutive catalytic reactions.
Request pdf synthesis and application of chiral monodentate phosphines in asymmetric hydrogenation chiral monodentate phosphines ligands were the first ligands to be investigated in the field. Enantiopure chiral phosphines bearing a sulfinyl group and. Furthermore, the synthesis of a new chiral amine functionalized nhc ligand is explored, which has potential applications as a ligand in the metalcatalyzed enantioselective hydrogenation of polar bonds. Enantioselective catalysis using pchiral phosphines and. Abstract the synthesis and design of new phosphines is a continuing area of interest. Synthesis and applications of pchirogenic and axially chiral p,n. Enantioselective synthesis of pchiral tertiary phosphine oxides with an ethynyl group via cuicatalyzed azidealkyne cycloaddition renyi zhu,a long chen,a xiaosi hu,a feng zhou ab and jian zhou abc we report the highly enantioselective synthesis of pchiral tertiary phosphine oxides featuring an ethynyl. The products were characterized by 1 h and 31 p nmr measurements. Reported here is a highly efficient and accelerated catalytic asymmetric synthesis of p. Enantioselective synthesis of planarchiral phosphines with 1,ndioxanparacyclophane scaffold and their application as chiral ligands. A novel method for the synthesis of chiral sulfonated. Airstable chiral primary phosphines part i synthesis, stability and applications rachel m.