Asymmetric hydrogenation catalyzed by rhodium complexes of 2,3-bis(dimenthylphosphino)maleic anhydride and 2,3-bis(dimenthylphosphino)-N-phenylmaleimide

Kinting, Annegret; Krause, H. W.

doi:10.1016/0022-328x(86)80090-0

Cited by 14 publications

(8 citation statements)

References 14 publications

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“…This approach was aided by parallel work in our laboratory on new and improved syntheses of dimenthylphosphino derivatives through building blocks that are readily available from (−)‐menthol [70–72] . Further considering that Men 2 P‐based ligands have so far only shown moderate inductions in asymmetric catalysis, [83–89] whereas tertiary phosphines bearing a single (neo)menthyl group have proven more successful, [90–93] we hoped to achieve even higher spatial asymmetry around the coordination sphere by working with mixed aryl(menthyl)phosphine donor‐groups. Chlorophosphines of the formula Men(R)PCl (with R=Men, Ph or 2‐methoxynaphthyl) were prepared from the corresponding phosphine oxides Men(R)POH by chloro‐de‐oxygenation with PCl 3 [94] .…”

Section: Resultsmentioning

confidence: 99%

New Access Routes to Privileged and Chiral Ligands for Transition‐Metal Catalyzed Hydrogen Autotransfer (Borrowing Hydrogen), Dehydrogenative Condensation, and Alkene Isomerization Reactions

Koller

Klein

Reinhardt

et al. 2021

Helvetica Chimica Acta

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A group of transition-metal catalyzed hydrogen moving reactions, encompassing hydrogen autotransfer (HAT; also called borrowing hydrogen, BH), dehydrogenative condensation (DHC) and alkene isomerization, displays high atom economy and relies on widely available starting materials. Such reactions have considerable potential for clean reaction design and application in sustainable synthesis. With the aim to develop and study synthetic applications of the title reactions, we have set up synthetic access routes to a toolbox of structurally varied ligands for and pincer complexes of some transition metals (cobalt, ruthenium, iridium) that are well established for the title reactions. Ligand target structures, for which often improved syntheses have been found, encompass 6,6'-dihydroxy-2,2'-bipyridine, 2(3-hydroxyphenyl)pyridines (as backbones for PCN pincers), 2(6-methylpyridine-2yl)pyridines (as backbones for PNN pincers) and 2(3-tolyl)pyridines (as backbones for PCN pincers). To support research towards asymmetric versions of the title reactions, we have prepared asymmetrically modified versions of well-established catalysts, including chiral, enantiopure versions of Milstein's PNN-ruthenium pincer, Kempe's triazinyl-diaminophosphanyl PNP-iridium-or -cobalt pincers, Huang's PCN-iridium pincers, and Grotjahn's alkene zipper complex. The strategy applied to 'chiral switching' relied on replacing symmetric dialkylphosphine donorgroups by dimenthylphosphine or aryl(menthyl)phosphine donor units. The resulting ligands or complexes have been structurally characterized, and the catalytic potential of the catalysts has been established in exploratory model reactions (transfer hydrogenation; diol to lactone dehydrogenative condensation; alkene isomerization). Several model reactions have been designed which will allow to study asymmetric catalytic hydrogen moving reactions.

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Section: Resultsmentioning

confidence: 99%

New Access Routes to Privileged and Chiral Ligands for Transition‐Metal Catalyzed Hydrogen Autotransfer (Borrowing Hydrogen), Dehydrogenative Condensation, and Alkene Isomerization Reactions

Koller

Klein

Reinhardt

et al. 2021

Helvetica Chimica Acta

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“…228 Other studies focused on the preparation of 132 type ligands bearing chiral dimenthylphosphino or phospholane substituents (Scheme 52). Ligands 134 and 135 bearing menthyl groups at the phosphorus atoms were tested in asymmetric hydrogenation and hydrosilylation reactions of unsaturated substrates (Rh) 229,230 and in Kumada cross-coupling (Ni and Pd) 230 though with a limited success. The performance of 134 in Ni-catalysed isomerisation of N-phenyl-cyclopent-3-en-carboxamide resulting from Ni-mediated addition of phenylisocyanate to cyclopentene was poor, too.…”

Section: Phosphine-amides Whose Amide Nitrogen Is a Part Of A Cyclementioning

confidence: 99%

Phosphino-carboxamides: the inconspicuous gems

Štěpnička

2012

Chem. Soc. Rev.

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Compounds combining phosphine and carboxamide moieties in their molecules have developed virtually unnoticed into a specific class of highly structurally versatile and tuneable donor molecules finding manifold use in various fields, particularly in coordination chemistry, biomedical sciences and in catalysis. In the latter field, some phosphinoamides became the real privileged ligands and an indispensable part of a standard toolbox for synthetic chemists. This critical review aims to give an overview of the multifaceted chemistry of such compounds, paying attention to both the fundamentals and recent developments in this continuously expanding field.

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“…H Uh ci" V Ü ber die Synthese eines chiralen Derivates von 1, des 2,3-Bis(dimenthylphosphino)maleinsäureanhy-drids, wurde vor kurzem von einer anderen A rbeits gruppe berichtet [4], Im folgenden soll nun die D ar stellung und Charakterisierung von (5S)-3,4-Bis(diphenylphosphino)-5-menthoxy-2(5 H)-furanon (2) beschrieben werden. Die D iastereom ere, die sich in der Konfiguration am C-Atom 5 des Fünfringes unterscheiden, können durch mehrfaches Um kristallisieren aus «-Hexan ge trennt werden.…”

Section: Phpunclassified

“…Damit sollte die Möglichkeit bestehen, aus 2 optisch aktive Rhodiumkomplexe darzustellen, die als asymmetrische Katalysatoren wirken können. (4) 30 g (0,18 mol) M ucochlorsäure, 28 g (0,18 mol) ( -)-M enthol und 0,9 g (5 mmol) p-Toluolsulfonsäure werden in 200 ml Toluol suspendiert und 7 h am W asserabscheider unter Rückfluß erhitzt. Nach dem Abkühlen auf R aum tem peratur wird das R eak tionsgemisch mit 100 ml 6 -proz.…”

Section: Tab I Atom Koordinaten Und Tem Peraturfaktoren Von 7 D Ieunclassified

Ein Beitrag zur Synthese neuer chiraler Phosphanliganden / Synthesis of a New Chiral Phosphine Ligand

Fenske

Merzweiler

1989

Zeitschrift Für Naturforschung B

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X -R ay, Chiral Phosphine, Nickel-Phosphine ComplexThe new chiral diphosphine 2 was synthesized from mucochloric acid. The structure o f the NiLcom plex 7 was determ ined by single crystal X-ray analysis. 7 crystallizes in the orthorhom bic space group P 2 ,2 |2 |. The lattice constants (at 180 K) are: a -914.1(2); b = 1422.0(3); c -4112.5(10) pm. N il 0,5792(1) 0,0959(1) 0,1174(1) 0.022(1) 11 0,5638(1) -0 ,0 7 4 7 (1 ) 0,1324(1) 0.034(1) 12 0,7326(1) 0,0690(1) 0,0677(1) 0.035(1) P l 0,4500(2) 0,1258(1) 0.1602(1) 0.020(1) P2 0,5844(2) 0,2433(1) 0,1055(1) 0.020(1) C I 0,4363(8) 0,2539(5) 0.1622(2) 0,020(2) C 2 0,4879(8) 0,3041(5) 0,1378(2) 0,018(2) C3 0,4683(8) 0,4087(5) 0.1451(2) 0,021(2) C 4 0,3669(9) 0,3180(6) 0,1862(2) 0,027(2) O l 0.3907(6) 0,4527(4) 0,1209(1) 0,022(2) 0 2 0,3838(6) 0,4069(4) 0,1754(1) 0,029(2) 0 3 0,3059(8) 0,3009(5) 0,2115(1) 0,040(2) C5 0,4018(9) 0,5563(5) 0,1204(2) 0,024(2) C 6 0,3258(9) 0,5876(6) 0,0892(2) 0.026(2) C 7 0,3219(11) 0,6945(6) 0,0885(2) 0,035(3) C8 0,2523(10) 0,7382(6) 0,1189(2) 0,036(3) C 9 0,3349(11) 0,7066(6) 0,1492(2) 0,035(3) CIO 0,3354(9) 0,5993(6) 0,1504(2) 0,029(2) C l l 0,3884(11) 0,5441(6) 0,0582(2) 0,037(3) C12 0,5367(11) 0,5815(7) 0,0488(2) 0,048(3) C13 0,2779(14) 0,5577(8) 0,0291(2) 0,055(4) C 14 0,2657(13) 0,7480(6) 0,1792(2) 0.047(3) C15 0,5317(8) 0,0948(5) 0,1988(2) 0,021(2) C 16 0,4893(11) 0,0129(7) 0,2150(2) 0.035(3) C17 0,5609(12) -0 ,0 1 0 7 (7 ) 0,2439(2) 0,042(3) C 18 0,6714(12) 0,0420(8) 0.2554(2) 0,045(4) C 19 0.7170(10) 0,1227(7) 0.2394(2) 0.038(3) C 20 0,6450(9) 0,1482(7) 0.2113(2) 0,030(3) C21 0,2618(9) 0,0860(6) 0,1599(2) 0.027(3) C22 0.2058(10) 0,0484(7) 0,1311(3) 0.040(3) C23 0.0583(13) 0,0189(8) 0,1303(4) 0.066(5) Tab. I. (Fortsetzung).

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Asymmetric hydrogenation catalyzed by rhodium complexes of 2,3-bis(dimenthylphosphino)maleic anhydride and 2,3-bis(dimenthylphosphino)-N-phenylmaleimide

Cited by 14 publications

References 14 publications

New Access Routes to Privileged and Chiral Ligands for Transition‐Metal Catalyzed Hydrogen Autotransfer (Borrowing Hydrogen), Dehydrogenative Condensation, and Alkene Isomerization Reactions

New Access Routes to Privileged and Chiral Ligands for Transition‐Metal Catalyzed Hydrogen Autotransfer (Borrowing Hydrogen), Dehydrogenative Condensation, and Alkene Isomerization Reactions

Phosphino-carboxamides: the inconspicuous gems

Ein Beitrag zur Synthese neuer chiraler Phosphanliganden / Synthesis of a New Chiral Phosphine Ligand

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