Attempted resolution of free (±)-chlorophenylisopropylphosphine

Pabel, Michael; Willis, Anthony C.; Wild, S. Bruce

doi:10.1016/0957-4166(95)00314-f

Cited by 36 publications

(4 citation statements)

References 18 publications

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“…As a hybrid of PC and deracemization, SOAT offers great promise as a process affording high yield and high productivity. To the best of our knowledge, there have been relatively few reports on the SOAT process and no studies have investigated the productivity of the process. − In the present study, we examined the application of the SOAT process to naphthamide 1 (Figure ), a conglomerate-forming system that exhibits solid-state atropisomerism (i.e., it spontaneously racemizes in solution) at two different scales. In addition, we show that SOAT of this compound is more productive than that of regular TCID even if the two processes are comparable in terms of interplay between homogeneous and heterogeneous equilibria …”

Section: Introductionmentioning

confidence: 99%

Resolution of an Atropisomeric Naphthamide by Second-Order Asymmetric Transformation: A Highly Productive Technique

Oketani

Hoquante

Brandel

et al. 2019

Org. Process Res. Dev.

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Temperature-cycle-induced deracemization (TCID) has been widely studied in the field of chiral separation, ranging from fundamental research to applications. In this study, the secondorder asymmetric transformation (SOAT) of 2-methoxy-1-naphthamide in an azeotropic mixture of ethyl acetate and cyclohexane is compared with TCID, in terms of process productivity. The results indicate that the volumetric productivity using SOAT was over 100times higher than that using TCID, such that a scale-up by a factor of 10 was easily implemented.

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Section: Introductionmentioning

confidence: 99%

Resolution of an Atropisomeric Naphthamide by Second-Order Asymmetric Transformation: A Highly Productive Technique

Oketani

Hoquante

Brandel

et al. 2019

Org. Process Res. Dev.

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“…Synthese, spektroskopische Untersuchung und Moleku È lstruktur von cis-rac-[Mo(CO) 4 {1,2-(PPhCl) 2 C 2 B 10 H 10 }] (2) Wir konnten bereits ku È rzlich zeigen, daû rac-1,2-Bis(chlorophenylphosphino)-1,2-dicarba-closo-dodecaboran (12) (1) [1,9] mit [PdCl 2 (COD)] (COD = Cyclooctadien) bei Raumtemperatur in einer glatten Reaktion zu cis-rac-[PdCl 2 {1,2-(PPhCl) 2 C 2 B 10 H 10 }] reagiert [7]. Hingegen setzt sich 1 mit [Mo(CO) 4 (m = 2034, 1955, 1936, 1905 cm ±1 ) [9] zu ho È heren Wellenzahlen verschoben, was fu È r eine sta È rkere Metall±Phosphor-Ru È ckbindung in 2 spricht.…”

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Koordinationseigenschaften von Carbaboranylchlorophosphanen: Synthese und Molekülstruktur voncis-rac-Molybdäntetracarbonyl{1,2-bis(chlorophenylphosphino)-1,2-dicarba-closo-dodecaboran(12)}

Balema

Blaurock

Hey‐Hawkins

1999

Z. anorg. allg. Chem.

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Coordination Properties of Carbaboranylchlorophosphines: Synthesis and Molecular Structure of cis‐rac‐Molybdenumtetracarbonyl{1,2‐bis(chlorophenylphosphino)‐1,2‐dicarba‐closo‐dodecaborane(12)} Rac‐1,2‐bis(chlorophenylphosphino)‐1,2‐dicarba‐closo‐dodecaborane(12) (1) reacts with [Mo(CO)4(NBD)] (NBD = norbornadiene) after several hours at 50–55 °C to yield cis‐rac‐[Mo(CO)4{1,2‐(PPhCl)2C2B10H10}] (2). 2 was characterised spectroscopically (1H, 13C, 11B and 31P NMR) and by crystal structure determination.

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“…The resolution of racemic ligands remains an active area of research due to the usefulness of the enantiomerically pure compounds in asymmetric catalysis. [60][61] The use of chiral cyclopalladeted complexes as resolving agents for resolution of phosphines and arsines have being employed by Wild et al [62][63][64][65][66] and Leung et al [67][68][69] .…”

Section: Resolution Of Phosphines and Arsinesmentioning

confidence: 99%

“…A series of enantiomerically pure ligands (76)(77)(78)(79)(80)(81) have being resolved using chiral palladacycle 13 (Scheme 1.24). [62][63][64][65][66][67][68][69]…”

Section: Resolution Of Phosphines and Arsinesmentioning

confidence: 99%

Design and synthesis of chiral organopalladium-amine complexes

Yap¹

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Bn benzyl Bu butyl br broad c concentration for optical rotation analysis calcd calculated conc. concentrated CDCl3 chloroform-d1 CD2Cl2 dichloromethane-d2 CHCl3 chloroform CH3CN acetonitrile Claisen's alkali a strong base prepared by 8.81 g KOH dissolved in 6 ml of XI Summary This thesis describes the design and synthesis of chiral organopalladium-amine complexes and their applications in stoichiometric asymmetric synthesis. A brief introduction on the organopalladium-amine complexes, the research development and the objective of this project were presented in Chapter 1. In Chapter 2, a functionalized amine, 1-(2,5-di-tert-butylphenyl)-N,Ndimethylethanamine was designed and synthesized, but the ortho-palladation reaction did not give the desired palladacycle. An unexpected C−N bond cleavage was observed and gave two C−N bond cleavage complexes. The mechanistic studies on the formation of C−N bond cleavage complex was carried out, but no substantial conclusion can be made yet. The initial step is likely β-hydride elimination and it is a base promoted reaction. Chapter 3 describes the synthesis of slightly less bulky amine ligand, 1-(2,5-diiso-propylphenyl)-N,N-dimethylethanamine from p-di-iso-propylbenzene. By optimizing the reaction conditions including replacement of some of the reagents, it resulted in increased of the overall yield of the amine ligand. The ortho-palladation reaction gave the desired palladacycle and C−N bond cleavage complex by varying the palladating agent used. The racemic dimeric complex was resolved by separation of the (S)-prolinate diastereomeric derivatives via column chromatography. The efficiency of the palladacycle was assessed via the asymmetric intramolecular endocycloaddition reaction and a better stereoselectivity was obtained. In chapter 4 describes the synthesis of an electron-withdrawing group functionalized benzyl palladacycle to investigate the electronic effect of the palladacycle in asymmetric Diel-Alder reaction. The amine ligand, 1-(2,5dichlorophenyl)-N,N-dimethylethanamine was synthesized via three step synthetic XII route with high overall yield and ortho-palladation with Pd(OAc)2 to give the acetatebridged dimeric palladacycle. The racemic dimer was resolved with optically active sodium prolinate and by treatment of the corresponding diastereomer with aqueous 1M HCl produced the chiral chloro-bridged dimer. The efficiency of the palladacycle was examined via Diels-Alder reaction between DMPP-coordinated complex and ethyl vinyl ketone, however poor stereoselectivity was observed. The chiral dimeric complex was converted to the cationic complex and used in asymmetric hydrophosphination reaction between diphenylphosphine and DMAD to give one diastereomeric product.

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Attempted resolution of free (±)-chlorophenylisopropylphosphine

Cited by 36 publications

References 18 publications

Resolution of an Atropisomeric Naphthamide by Second-Order Asymmetric Transformation: A Highly Productive Technique

Resolution of an Atropisomeric Naphthamide by Second-Order Asymmetric Transformation: A Highly Productive Technique

Koordinationseigenschaften von Carbaboranylchlorophosphanen: Synthese und Molekülstruktur voncis-rac-Molybdäntetracarbonyl{1,2-bis(chlorophenylphosphino)-1,2-dicarba-closo-dodecaboran(12)}

Design and synthesis of chiral organopalladium-amine complexes

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