Asymmetric Reductive Coupling of Dienes and Aldehydes Catalyzed by Nickel Complexes of Spiro Phosphoramidites:  Highly Enantioselective Synthesis of Chiral Bishomoallylic Alcohols

Yang, Yun; Zhu, Shou‐Fei; Duan, Haifeng; Zhou, Chang‐Yue; Wang, Lixin; Zhou, Qi‐Lin

doi:10.1021/ja0693183

Cited by 146 publications

(41 citation statements)

References 21 publications

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“…[19] In the presence of (R)-1 a, the NÀH insertion reaction proceeded within 5 minutes to afford the insertion product in excellent yield with 11 % ee ( Table 1, entry 2). Control experiments showed that the SPAs alone did not promote the insertion reaction.…”

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confidence: 99%

Asymmetric NH Insertion Reaction Cooperatively Catalyzed by Rhodium and Chiral Spiro Phosphoric Acids

et al. 2011

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Nitrogen-containing organic compounds, such as a-amino acids and alkaloids, are important biologically active compounds, thus the development of efficient and enantioselective methods for the construction of carbon-nitrogen bonds is a fundamental goal in modern organic synthesis.[1] Transitionmetal-catalyzed carbene insertion into N À H bonds is one of the most efficient methods to construct carbon-nitrogen bonds [2] and the development of asymmetric versions of the NÀH insertion reaction has attracted considerable attention. [3] In initial studies, chiral dirhodium catalysts were tested in intramolecular [4] and intermolecular [5] NÀH insertion reactions, however, only low to modest enantioselectivities (< 50 % ee) were achieved. Since these reports, other transition metals including copper and silver have been used as catalysts, and gave enantioselectivities up to 48 % ee.[6]Recently, we reported a highly enantioselective NÀH insertion reaction (up to 98 % ee) using a copper complex with chiral spiro bisoxazoline ligands.[7] Subsequently, two other types of chiral copper catalysts have been developed, one with a planar chiral bipyridine ligand [8] and the other with a binolderivative ligand, [9] and both of these catalysts give high enantioselectivities in NÀH insertion reactions.Although progress on copper-catalyzed asymmetric NÀH insertion reactions has been substantial, they still have serious limitations. For instance, all the copper-catalyzed N À H insertion reactions require high catalyst loading (5-10 mol %) for satisfactory yields and enantioselectivities, thus more-efficient chiral catalysts are highly desirable. Because the activity of dirhodium(II) catalysts is usually superior to that of copper catalysts in nonenantioselective NÀ H insertion reactions, [10] the possibility of using dirhodium catalysts to achieve highly enantioselective N À H insertion reactions is an intriguing one. Recently, Saito et al. [11] reported that dirhodium(II) carboxylates and cinchona alkaloids cooperatively catalyze the asymmetric NÀH insertion reactions of a-diazo-a-arylacetates with anilines. The combined catalysts exhibit excellent reactivity but only modest enantioselectivity (up to 71 % ee). It is generally accepted that the rhodium-catalyzed N À H insertion most likely proceeds via an ylide intermediate (Scheme 1 A).[2a] We speculated that the subsequent protontransfer step could be facilitated by a chiral phosphoric acid [12] species via a seven-membered-ring transition state, and that, consequently, chiral induction could be accomplished in this step (Scheme 1 B). The groups of Yu [13] and Platz [14] have reported that either water or alcohols can assist proton transfer in OÀH insertion reactions, as indicated by density functional theory calculations and ultrafast time-resolved IR spectroscopy studies. These studies stimulated our interest in exploring asymmetric N À H insertion in the presence of a proton-transfer catalyst. As part of our ongoing work on the development of asymmetric carbene insertion reaction...

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Asymmetric NH Insertion Reaction Cooperatively Catalyzed by Rhodium and Chiral Spiro Phosphoric Acids

et al. 2011

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“…Corresponding ketone homoallylations were developed using diethylzinc as terminal reductant (21). Asymmetric variants of the nickel-catalyzed diene-aldehyde reductive couplings are limited to 1,4-diaryl-butadienes (22, 23). Whereas rhodium-catalyzed diene-carbonyl reductive coupling mediated by elemental hydrogen require use of α-ketoaldehydes (24), ruthenium catalysts promote the reductive coupling of diverse dienes to unactivated aldehydes via transfer hydrogenation (25).…”

Section: Dienes and Enynesmentioning

confidence: 99%

Metal-catalyzed reductive coupling of olefin-derived nucleophiles: Reinventing carbonyl addition

Nguyen

Park

Luong

et al. 2016

Science

325

120

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α-Olefins are the most abundant petrochemical feedstock beyond alkanes, yet their use in commodity chemical manufacture is largely focused on polymerization and hydroformylation. The development of byproduct-free catalytic C-C bond forming reactions that convert olefins to value-added products remains an important objective. Here, we review catalytic intermolecular reductive couplings of unactivated and activated olefin-derived nucleophiles with carbonyl partners. These processes represent an alternative to the longstanding use of stoichiometric organometallic reagents in carbonyl addition.

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“…The Mori-Tamaru nickel-catalyzed coupling of 1,3-dienes and aldehydes (Scheme 11) [39] was chosen because this three-component coupling offers several distinct challenges with respect to the ligand system that were not examined in the gold(I)-catalyzed reaction; 1) unlike the gold(I)-catalyzed cyclohydroamination reaction, the coordinated nickel atom undergoes a change in the oxidation state in this transformation, 2) this transformation gives rise to two stereocenters and thus is potentially dia-and enantioselective, 3) the nickel-catalyzed reaction involves more aggressive reagents than the previously explored gold(I) reaction, and 4) this transformation is known to be catalyzed by complexes containing monodentate phosphorus ligands. [40] The asymmetric intermolecular version of the nickel-catalyzed coupling reaction was first reported by Zhou et al in 2007 by using substituted spirobiindane phosphoramidite ligands. [41][42][43] The reaction proceeds through an oxidative cyclometallation, forming an allylalkoxynickel(II) intermediate, which is subsequently re-reduced to the catalytically active nickel(0) species.…”

Section: Wwwchemeurjorgmentioning

confidence: 99%

Chiral Ditopic Cyclophosphazane (CycloP) Ligands: Synthesis, Coordination Chemistry, and Application in Asymmetric Catalysis

Roth

Wadepohl

Wright

et al. 2013

Chemistry A European J

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A series of dichlorocyclophosphazanes [{ClP(μ-NR)}2 ] containing chiral and achiral R groups was obtained from simple commercially available amines and PCl3 . Their condensation reactions with axially chiral biaryl diols yielded ansa-bridged chiral cyclophosphazane (CycloP) ligands. This highly modular methodology allows extensive elaboration of the ligand set, in which the chirality can be introduced at the diol bridge and/or the amido R group. This provides the possibility to observe match and mismatch effects in catalysis. A series of twenty CycloP ligands was synthesized and characterized by multinuclear NMR spectroscopy, HRMS, elemental analysis, and in selected cases, single-crystal X-ray diffraction. These studies show that all of the ditopic CycloP ligands are C2 symmetric, rendering their metal coordination sites symmetry equivalent. Two well-established enantioselective reactions were explored by using late-transition metal CycloP complexes as catalysts; the gold-catalyzed hydroamination of γ-allenyl sulfonamides and the asymmetric nickel-catalyzed three-component coupling of a diene and an aldehyde. The steric demands of the CycloP ligands have a subtle influence on the reactivity and selectivity observed in both reactions. Good enantiomeric ratios (e.r.) as high as 89:11 in the gold-catalyzed reaction and 92:8 in the nickel-catalyzed bis-homoallylation reaction were observed.

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Asymmetric Reductive Coupling of Dienes and Aldehydes Catalyzed by Nickel Complexes of Spiro Phosphoramidites: Highly Enantioselective Synthesis of Chiral Bishomoallylic Alcohols

Cited by 146 publications

References 21 publications

Asymmetric NH Insertion Reaction Cooperatively Catalyzed by Rhodium and Chiral Spiro Phosphoric Acids

Asymmetric NH Insertion Reaction Cooperatively Catalyzed by Rhodium and Chiral Spiro Phosphoric Acids

Metal-catalyzed reductive coupling of olefin-derived nucleophiles: Reinventing carbonyl addition

Chiral Ditopic Cyclophosphazane (CycloP) Ligands: Synthesis, Coordination Chemistry, and Application in Asymmetric Catalysis

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