Chiral Ferrocenylphosphine Research Articles

A Concise Update on the Applications of Chiral Ferrocenyl Phosphines in Homogeneous Catalysis Leading to Organic Synthesis

AbstractFor Abstract see ChemInform Abstract in Full Text.

A concise update on the applications of chiral ferrocenyl phosphines in homogeneous catalysis leading to organic synthesis.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTA Concise Update on the Applications of Chiral Ferrocenyl Phosphines in Homogeneous Catalysis Leading to Organic SynthesisThomas J. ColacotView Author Information Organometallic Chemicals & Catalysts Development, Johnson Matthey Catalysts, 2001 Nolte Drive, West Deptford, New Jersey 08066 Cite this: Chem. Rev. 2003, 103, 8, 3101–3118Publication Date (Web):July 29, 2003Publication History Received11 February 2003Published online29 July 2003Published inissue 1 August 2003https://doi.org/10.1021/cr000427oCopyright © 2003 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views3509Altmetric-Citations454LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit Read OnlinePDF (423 KB) Get e-AlertsSUBJECTS:Catalysts,Chirality,Group 15 compounds,Hydrogenation,Ligands Get e-Alerts

A Novel Chiral Ferrocenyl Phosphine Ligand from Sugar: Applications in Rh‐Catalyzed Asymmetric Hydrogenation Reactions.

AbstractFor Abstract see ChemInform Abstract in Full Text.

光学活性フェロセンおよびその誘導体の新規合成法と不斉合成反応への応用

A classical route to chiral ferrocenes is optical resolution of the racemate and limited compounds have been prepared by this method. Recent successes in the synthesis of a variety of chiral ferrocenes without optical resolution now have attracted considerable attention in asymmetric synthesis. The chiral ferrocenylalcohols, -amines, -acetals, and-oxazolines can be readily prepared from achiral acyl-, formylferrocenes, and ferrocenecarboxylic acids. These substituents attached to cyclopentadienyl group of ferrocenes are strong ortho directing groups which lead to planar chiral ferrocenes with highly regioselection (>99% de). The planar chiral ferrocene can be also prepared by enantioselective lithiation of the achiral ferrocenylamide and amine with the chiral lithium reagent. C2 symmetrical 1, 1'-ferrocenediol is obtained from asymmetric reduction of 1, 1'-diacyl ferrocene and can be converted to the corresponding ferrocenediamine and-diphosphine derivatives. New planar chiral ferrocenyl phosphines and alcohols are examined in the benchmark asymmetric allylic substitution and dialkylzinc addition to an aldehyde, respectively.

A novel chiral ferrocenyl phosphine ligand from sugar: applications in Rh-catalyzed asymmetric hydrogenation reactions.

[structure: see text] A new chiral ferrocenyl diphosphine ligand 3 was synthesized from readily available D-mannitol. Rh-complex with this ligand showed high enantioselectivity and reactivity in the asymmetric hydrogenation of dehydroamino acid derivatives and itaconic acid derivatives. Up to over 99% ee and 10 000 TON were achieved with this catalytic system.

Studies on the asymmetric synthesis of huperzine A. Part 2: Highly enantioselective palladium-catalyzed bicycloannulation of the β-keto-ester using new chiral ferrocenylphosphine ligands

New chiral ferrocenylphosphine ligands were designed and tested in the enantioselective bicycloannulation of β-keto-ester 2 with bifunctional allylic agent 4. A range of e.e. values from 80 to 90% of the bicyclic intermediate 6 was achieved. Subsequently, enantiopure (−)-huperzine A was prepared in ca. 40% yield from β-keto-ester 2.

ChemInform Abstract: Synthesis of Silica-Supported Chiral Ferrocenylphosphine Ligands and Their Application in Some Stereoselective Reactions.

Synthesis of new BPPFA analogues, having exchanged one of the N-methyl groups for a long (–C10H20–) or short (–C4H8–) alkyl chain with a terminal methoxycarbonyl group, and their immobilization on silica are described. Immobilization resulted in considerable lowering of the reaction rates as well as stereoselectivity in hydrogenation reactions. On the other hand, both homogeneous 3a as well as immobilized ligand 6a with a longer spacer (–C10H20–) have activities and enantioselectivities in allylic nucleophilic substitution comparable to the known BPPFA ligand. This is true also for homogeneous ligand 3b with a shorter chain (–C4H8–), but its immobilization resulted in a big drop of activity as well as selectivity.

Atropselective alkylation of biaryl compounds by means of transition metal-catalyzed C–H/olefin coupling

The reaction of 2-(1-naphthyl)-3-methylpyridine with olefins in the presence of [RhCl(coe)2]2 and PCy3 as the catalyst resulted in the alkylation of the naphthyl ring at the 2-position in good yield. The replacement of PCy3 with the chiral ferrocenyl phosphine, (R),(S)-PPFOMe, as the ligand resulted in atropselective alkylation of the naphthylpyridine derivatives. Ethylene reacted with the biaryl compounds to give the corresponding addition products in moderate yields with fair to good ee's (up to 49% ee).

Synthesis of silica-supported chiral ferrocenylphosphine ligands and their application in some stereoselective reactions

Synthesis of new BPPFA analogues, having exchanged one of the N-methyl groups for a long (–C10H20–) or short (–C4H8–) alkyl chain with a terminal methoxycarbonyl group, and their immobilization on silica are described. Immobilization resulted in considerable lowering of the reaction rates as well as stereoselectivity in hydrogenation reactions. On the other hand, both homogeneous 3a as well as immobilized ligand 6a with a longer spacer (–C10H20–) have activities and enantioselectivities in allylic nucleophilic substitution comparable to the known BPPFA ligand. This is true also for homogeneous ligand 3b with a shorter chain (–C4H8–), but its immobilization resulted in a big drop of activity as well as selectivity.

Synthetic studies of huperzine A and its fluorinated analogues. 1. Novel asymmetric syntheses of an enantiomeric pair of huperzine A

Syntheses of an enantiomeric pair of huperzine A were accomplished by employing two types of methods which feature the tandem Cinchona alkaloids-promoted asymmetric Michael addition / aldol reaction of the β-keto ester 3 with methacrolein ( 4) (max. 64% ee, 3+4→5 , Scheme 2) and the asymmetric bicycloannulation of 3 with 2-methylene-1,3-propanediol diacetate ( 7) catalyzed by palladium catalysts carrying chiral ferrocenylphosphine ligands (max. 64% ee, 3+7→8 , Scheme 3) as the key steps. Recrystallization of the partially optically active tricycles (+)- and (−)- 6 derived from the products of the asymmetric reactions, readily provided the corresponding optically pure samples (both >99% ee). According to the reported method, the total synthesis of an enantiomeric pair of 1 [(−)- and (+)- 1] was completed starting with optically pure (+)- and (−)- 6 ( Scheme 4).

New chiral ligands for the asymmetric copper catalyzed conjugate addition of Grignard reagents to enones

The copper catalyzed conjugate addition of n-butyl Grignard to enones in the presence of chiral ferrocenyl phosphine oxazoline ligands has been studied and found to provide useful levels of asymmetric induction. A comparison of the ferrocene derived ligands 3 and 6 with the corresponding phenyl derived ligands 8 and 9 reveals that the ferrocene template plays an essential role in the reaction.

Catalytic asymmetric hydrosilylation of ketones with new chiral ferrocenylphosphine-imine ligands

Abstract New chiral ferrocenylphosphines containing an imino group on the side chain, (S)-N-alkylidene-1-[(R)-2-diphenylphosphinoferrocenyl]ethylamines, were prepared by condensation of (S)-1-[(R)-2-diphenylphosphinoferrocenyl]ethylamine with aromatic aldehydes. The imino-phosphine ligands were found to be very effective for rhodium-catalyzed asymmetric hydrosilylation of prochiral ketones with diphenylsilane to give optically active alcohols of up to 90% ee.

Preparation and use of chiral ferrocenylphosphines containing new alkyl substituents on the ferrocenylmethyl position

Abstract New homochiral ferrocenylphosphines, (Et-PPFA 5a), (Et-BPPFA 6a), and (Bu-BPPFA 6b), containing an ethyl or butyl group on the ferrocenylmethyl position were prepared by way of stereoselective ortho lithiation of (R)-N,N-dimethyl-1-ferrocenylpropylamine (4a) or its pentylamine analogue 4b, the lithiation proceeding with high (>99%) diastereoselectivity. Ethyl-substituted ferrocenylmonophosphine (Et-PPFA 5a) and ferrocenylbisphosphine (Et-BPPFA 6a) were found to be more effective as chiral ligands than the methyl-substituted ferrocenylphosphines, PPFA 1 and BPPFA 2, respectively, for some catalytic asymmetric reactions including nickel-catalyzed cross-coupling and palladium-catalyzed allylic silylation.

Highly Efficient One-Step Preparation of 1-Ferrocenylbenzylamine via Titanium(IV) Isopropoxide Mediated Reductive Amination of Benzoylferrocene

Abstract An efficient single-step synthesis of 1-ferrocenylbenzylamine, an effective chiral template in asymmetric four component peptide synthesis and immediate precursor to a variety of chiral ferrocenylphosphine ligands has been developed via reductive amination of benzoylferrocene using titanium(IV) isopropoxide and sodium borohydride.

Multidimensional 109Ag, 31P, and 1H HMQC and HSQC NMR studies on a model homogeneous catalyst. Reactions of a chiral ferrocenylphosphine with Ag(CF3SO3)

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTMultidimensional 109Ag, 31P, and 1H HMQC and HSQC NMR studies on a model homogeneous catalyst. Reactions of a chiral ferrocenylphosphine with Ag(CF3SO3)Francesca Lianza, Alceo Macchioni, Paul Pregosin, and Heinz RueggerCite this: Inorg. Chem. 1994, 33, 22, 4999–5002Publication Date (Print):October 1, 1994Publication History Published online1 May 2002Published inissue 1 October 1994https://doi.org/10.1021/ic00100a025RIGHTS & PERMISSIONSArticle Views249Altmetric-Citations18LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (443 KB) Get e-Alerts Get e-Alerts

Synthesis and structure of new chiral ferrocenylphosphines for asymmetric catalysis

The reaction of ( R)-1-[( S)-(diphenylphosphino)ferrocenyl]ethyl acetate ( 1) or N,N-dimethyl-( R)-1-[( S)-(diphenylphosphino)ferrocenyl]ethylamine ( 2a) with secondary phosphines in acetic acid leads to the diphosphines 5 in moderate to good yields. Two of these ligands, ( R)=1[( S)-(diphenylphosphino)ferrocenyl]ethyl-dicyclohexylphosphine ( 5a) and ( R P , R)-1[( S)-(diphenylphosphino)ferrocenyl]ethyl-phenyl-(2-methoxyphenyl)phosphine ( 5g), as well as the complexes [Rh( 5a)(NBD)]BF 4·2CH 2Cl 2 ( 9), [Pd(η 3-C 3H 5) ( 5a)]OTf ( 10) and [PtCl 2( 5a)] ( 11), have been characterized by X-ray diffraction. Crystals of 5a, 9, 10 and 11 are orthorhombic, space group P2 12 12 1, with four molecules in the unit cell. 5a: a=10.772(1), b=15.278(1), c=21.069(2) Å; 9: a=18.166(2), b=17.540(2), c=14.564(1); 10: a=10.995(4), b=14.021(8), c=25.410(11) Å; 11: a=15.077(14), b=15.122(16), c=16.188(11) Å. The stereogenic-at-phosphorus derivative 5g crystallizes in the monoclinic system, space group P2 1, with two pairs of symmetry independent molecules per the unit cell with a=7.896(1), b=25.667(2), c=15.654(1) Å and β=92.39(1)°. Very similar conformations of the chelate rings in the complexes 9–11 are observed, this being indicative of the relative rigidity of the ligand 5a.

Thiolato ligands derived from chiral ferrocenylphosphines: synthesis and structure of the trimeric copper(I) complex [{(R)-(S)-CpFe(.eta.5-C5H3(1-PPh2)(2-CH(CH3)S))}Cu

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTThiolato ligands derived from chiral ferrocenylphosphines: synthesis and structure of the trimeric copper(I) complex [{(R)-(S)-CpFe(.eta.5-C5H3(1-PPh2)(2-CH(CH3)S))}Cu]3Antonio Togni, Grety Rihs, and Ruth E. BlumerCite this: Organometallics 1992, 11, 2, 613–621Publication Date (Print):February 1, 1992Publication History Published online1 May 2002Published inissue 1 February 1992https://doi.org/10.1021/om00038a019RIGHTS & PERMISSIONSArticle Views189Altmetric-Citations34LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (2 MB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

Asymmetric synthesis catalyzed by chiral ferrocenylphosphine transition metal complexes. 10 gold(i)-catalyzed asymmetric aldol reaction of isocyanoacetate

Optically active ferrocenylbisphosphine ligands containing 2-(dialkylamino)ethylamino group on the ferrocenylmethyl position have been prepared and used for the gold(I)-catalyzed asymmetric aldol reaction of isocyanoacetate with aldehydes. Six-membered ring amines, such as morpholino or piperidino group, at the terminal of the side chain were most stereoselective to give optically active trans-4- methoxycarbonyl-5-alkyl-2-oxazolines (up to 97% ee) with high enantio- and diastereoselectivity in a quantitative yield.

ChemInform Abstract: Application of the Gold(I)‐Catalyzed Aldol Reaction to a Stereoselective Synthesis of (2S,3R,4R,6E)‐3‐Hydroxy‐4‐methyl‐2‐(methylamino)oct‐6‐enoic Acid (= MeBmt). Cyclosporin′s Unusual Amino Acid.

The title compound 8 was prepared in three steps starting from the optically pure aldehyde (2R, 4E)-2-methyl-hex-4-enal (3), thus constituting the shortest synthetic approach reported. Two of the three stereogenic centers in the product were generated in a coupling reaction of 3 with ethyl isocyanoacetate, catalyzed by a gold(I)/chiral ferrocenylphosphine system, giving the dihydrooxazole 5 in 85% diastereoselectivity (mismatchedcase). The weak effect of double stereodifferentiation in this reaction (matched case 90% ds) is discussed. N-Methylation and hydrolytic ring opening of 5 gave the protected form 7 of MeBmt, The X-ray diffraction study carried out on 7 confirms the absolute configuration of the two stereogenic centers formed in the gold(I)-catalytic reaction.

Asymmetric allylic amination catalyzed by chiral ferrocenylphosphine-palladium complexes

A palladium complex bearing chiral (hydroxyalkyl)ferrocenylphosphine ligand was found to be a highly regio-and stereoselective catalyst for the asymmetric allylic amination of 2-butenyl acetates with benzylamine, the nucleophilic attack of the amine taking place selectively on the more substituted end of the π-allylpalladium intermediate to give optically active 3-benzyamino- 1-butene of up to 84% ee.