Enantioselective Cu-catalyzed 1,4-additions of organozinc and Grignard reagents to enones: exceptional performance of the hydrido-phosphite-ligand BIFOP-H

Brüllingen, Eric; Neudörfl, Jörg‐Martin; Goldfuß, Bernd

doi:10.1039/c8nj05886e

Cited by 8 publications

(6 citation statements)

References 108 publications

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“…As in related secondary phosphine complexes, − binding to copper resulted in coordination chemical shifts and increases in 1 J PH , which were larger in cations 6 – 9 than in neutral 10 – 13 (Table ). The 31 P{ 1 H} NMR signals were broadened by the 63 Cu and 65 Cu quadrupoles, and in some cases from exchange processes, which are described in more detail below.…”

Section: Resultsmentioning

confidence: 99%

“…The enhanced reactivity of the P–H bond in metal complexes of secondary phosphines has been exploited in both stoichiometric and catalytic P-alkylation . Coordination of secondary phosphines to labile Cu(I), as in cation A and neutral halide complexes B (Scheme ), is potentially useful because rapid ligand substitution increases catalytic turnover frequency, limits product inhibition, and enables dechelation of macrocycles formed via P-alkylation . For example, deprotonation/alkylation of C yielded macrocycle D , which was removed from copper as the phosphine oxide using H 2 S in air .…”

Section: Introductionmentioning

confidence: 99%

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Diastereoselective Coordination of P-Stereogenic Secondary Phosphines in Copper(I) Chiral Bis(phosphine) Complexes: Structure, Dynamics, and Generation of Phosphido Complexes

et al. 2019

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Diastereoselective coordination of racemic secondary phosphines (PHRR′) to Cu(I) precursors containing chiral bis(phosphines) (diphos*) was explored as a potential route to P-stereogenic phosphido complexes. Reaction of [Cu(NCMe) 7); two of the three expected isomers of the bis(secondary phosphine) complexes [Cu((R,R)i-Pr-DuPhos)(PhHP(CH 2 ) n PHPh)][PF 6 ] (n = 2 (8); n = 3 (9)) were formed preferentially in related reactions. Reaction of the halide-bridged dimers [Cu((R,R)-i-Pr-DuPhos)(X)] 2 or [Cu((R,R)-Me-FerroLANE)(I)] 2 with PHMe(Is) gave the labile adducts Cu((R,R)-i-Pr-DuPhos)(PHMe(Is))(X) (X = Cl (10), Br (11), I (12)) and Cu((R,R)-Me-FerroLANE)(PHMe-(Is))(I) (13). Complexes 1, 6, and 8−11 were structurally characterized by X-ray crystallography. Variable temperature NMR studies of 6 and 8 showed that the secondary phosphine ligands underwent reversible dissociation. Deprotonation of 6 or 7 generated the P-stereogenic phosphido complexes Cu(diphos*)(PMeIs) (diphos* = (R,R)-i-Pr-DuPhos ( 14) or (R,R)-Me-FerroLANE) (17)), observed by 31 P NMR spectroscopy, but decomposition also occurred. Density functional theory calculations were used to characterize the diastereomers of thermally unstable 17 and the inversion barrier in a model copperphosphido complex. These observations provided structure−property relationships which may be useful in developing catalytic asymmetric reactions involving secondary phosphines and P-stereogenic copper phosphido intermediates.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Diastereoselective Coordination of P-Stereogenic Secondary Phosphines in Copper(I) Chiral Bis(phosphine) Complexes: Structure, Dynamics, and Generation of Phosphido Complexes

et al. 2019

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“…An attempt to use the same ligand L19 in a Cu-catalysed 1,4-addition of R 2 Zn or RMgBr (R = Me, Et) to enones was unsuccessful; it was suggested that L19 was unstable under the reaction conditions used [51]. An attempt to use the same ligand L19 in a Cu-catalysed 1,4-addition of R2Zn or RMgBr (R = Me, Et) to enones was unsuccessful; it was suggested that L19 was unstable under the reaction conditions used [51].…”

Section: Other Catalytic Reactions With Monofluorophosphite Ligandsmentioning

confidence: 99%

“…The R 2 PCl route has the advantage of the ready availability of chlorophosphines from PCl 3 but the Cl 2 PF route can provide access to R 2 PF for which the corresponding R 2 PCl is unknown, as demonstrated for (PhC≡C) 2 PF [52]. An attempt to use the same ligand L19 in a Cu-catalysed 1,4-addition of R2Zn or RMgBr (R = Me, Et) to enones was unsuccessful; it was suggested that L19 was unstable under the reaction conditions used [51].…”

Section: Synthesis and Stability Of Monofluorophosphinesmentioning

confidence: 99%

Monofluorophos–Metal Complexes: Ripe for Future Discoveries in Homogeneous Catalysis

Miles-Hobbs,

Pringle,

Woollins

et al. 2024

Molecules

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The discovery that cyclic (ArO)2PF can support Rh-catalysts for hydroformylation with significant advantages in tuning regioselectivity transformed the study of metal complexes of monofluorophos ligands from one of primarily academic interest to one with potentially important applications in catalysis. In this review, the syntheses of monofluorophosphites, (RO)2PF, and monofluorophosphines, R2PF, are discussed and the factors that control the kinetic stability of these ligands to hydrolysis and disproportionation are set out. A survey of the coordination chemistry of these two classes of monofluorophos ligands with d-block metals is presented, emphasising the bonding of the fluorophos to d-block metals, predominantly in low oxidation states. The application of monofluorophos ligands in homogeneous catalysis (especially hydroformylation and hydrocyanation) is discussed, and it is argued that there is great potential for monofluorophos complexes in future catalytic applications.

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“…Recently, an enantioselective Cu(I) or Cu(II) catalyzed conjugate addition of dialkylzinc to enones and cyclohexenone were reported using fencholate-based phosphorus ligands, e. g. biphenyl-2,2'-bisfenchyl hydrido phosphate (BIFOPÀ H) (Scheme 20). [35] The 1,4-addition of Et 2 Zn to enones catalyzed by CuCl • BIFOPÀ H yields up to 93 % and 99 % ee. Interestingly, CuCl gave better enantioselectivity in 1,4-additions to enones (CuCl: 76 % ee; Cu(OTf) 2 : 49 % ee; CuCl 2 : 42 % ee) while Cu(OTf) 2 was found better in 1,4-additions to cyclohexenone (Cu(OTf) 2 : 65 % ee; CuCl: 20 % ee).…”

Section: Copper-catalyzed Asymmetric Conjugate Additionmentioning

confidence: 99%

Alkylation of Electron‐Deficient Olefins through Conjugate Addition of Organozinc Reagents: An Update

Baruah¹,

Deb

2021

Eur J Org Chem

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This review focuses on the applications of organozinc reagents in conjugate addition reactions. Organozinc compounds are a class of organometallic reagent used in various reactions such as addition, substitution, and coupling reactions. The conjugate addition or 1, 4-addition is one of the most useful bond forming strategies used in organic synthesis since broad range of nucleophiles can be employed in the reaction. Addition of organozinc to electron-deficient olefins attracts synthetic chemists as it preferably undergoes conjugate addition over 1,2addition unlike other organometallic reagents, such as Grignard reagent or organolithium. Many natural products were also synthesized by applying the conjugate addition reaction of organozinc. Moreover, organozinc reagents have superior functional group compatibility and can be easily prepared relative to other organometallic compounds. Consequently, conjugate additions of organozinc reagents were highly studied and having a review on it is very important at present. Though a few reviews are available, they either do not focus directly on the organozinc reagents or not on the conjugate addition. We hope that this review article will be of great use to organic researchers.

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Enantioselective Cu-catalyzed 1,4-additions of organozinc and Grignard reagents to enones: exceptional performance of the hydrido-phosphite-ligand BIFOP-H

Abstract: Enantioselective CuI-catalyzed 1,4-additions and DFT computations concerning the enantioselective mechanism.

Cited by 8 publications

References 108 publications

Diastereoselective Coordination of P-Stereogenic Secondary Phosphines in Copper(I) Chiral Bis(phosphine) Complexes: Structure, Dynamics, and Generation of Phosphido Complexes

Diastereoselective Coordination of P-Stereogenic Secondary Phosphines in Copper(I) Chiral Bis(phosphine) Complexes: Structure, Dynamics, and Generation of Phosphido Complexes

Monofluorophos–Metal Complexes: Ripe for Future Discoveries in Homogeneous Catalysis

Alkylation of Electron‐Deficient Olefins through Conjugate Addition of Organozinc Reagents: An Update

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