Rhodium‐Catalyzed Asymmetric Intramolecular Hydroamination of Unactivated Alkenes

Shen, Xiaoqiang; Buchwald, S. L.

doi:10.1002/anie.200905402

Cited by 168 publications

(12 citation statements)

References 65 publications

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“…(Hetero)aromatic amines have privileged scaffolds which are widely found in natural products, pharmaceuticals, dyes, and industrial fine chemicals. − Hydroamination through intra- and intermolecular addition of amine N–H bonds to alkenes is an attractive strategy with which to construct new C–N bonds and manipulate (hetero)aryl amines, owing to the widespread availability of alkenes (Scheme a). Although regioselective hydroamination via Markovnikov or anti-Markovnikov process is challenging, significant progress has been made in producing linear or branched amines based on transition-metal catalysis . Since aromatic amines are usually obtained from reduction of nitro(hetero)arenes, direct use of nitro(hetero)arenes as nitrogenous partners for the C–N coupling has the great advantage of step economy and easy manipulation, which can offer an appealing process for the construction of C–N bonds.…”

Section: Introductionmentioning

confidence: 99%

Iron-Catalyzed Reductive Coupling of Nitroarenes with Olefins: Intermediate of Iron–Nitroso Complex

et al. 2019

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Using a single half-sandwich iron(II) compound, Cp*Fe(1,2-Ph 2 PC 6 H 4 S)(NCMe) (Cp* − = C 5 Me 5 − , 1) as a catalyst, reductive coupling of nitroarenes with olefins has been achieved by a well-defined iron(II)/(EtO) 3 SiH system. Through either inter-or intramolecular reductive coupling, various branched amines and indole derivatives have been directly synthesized in one-pot. Mechanistic studies showed that the catalysis is initiated by activation of nitroarenes by the iron(II) catalyst with silane, generating iron−nitrosoarene intermediate for the C−N bond coupling.

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Section: Introductionmentioning

confidence: 99%

Iron-Catalyzed Reductive Coupling of Nitroarenes with Olefins: Intermediate of Iron–Nitroso Complex

et al. 2019

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“…Asymmetric hydroamination of alkenes is a desirable atom-economic route to introduce nitrogen-based functionalities into organic molecules. [10][11][12] Enzymatic addition of ammonia or amines to appropriate α,βunsaturated mono-or dicarboxylic acids using CÀ N lyases as biocatalysts has become an attractive methodology to synthesize chiral α-amino acids, such as phenylalanine and aspartic acid, and their derivatives (Scheme 1). [10,[13][14][15] This enzymatic strategy employs readily available α,β-unsaturated acids as starting materials, escaping steps of protecting/activating carboxylic groups by derivatization as the corresponding esters or amides, and normally gives high stereocontrol under mild and potentially green reaction conditions.…”

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confidence: 99%

Biocatalytic Enantioselective Hydroaminations for Production of N‐Cycloalkyl‐Substituted L‐Aspartic Acids Using Two C−N Lyases

Zhang

Tepper

et al. 2019

Adv Synth Catal

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N-cycloalkyl-substituted amino acids have wide-ranging applications in pharma-and nutraceutical fields. Here we report the asymmetric synthesis of various N-cycloalkyl-substituted laspartic acids using ethylenediamine-N,N'-disuccinic acid lyase (EDDS lyase) and a previously engineered variant of methylaspartate ammonia lyase (MAL-Q73A) as biocatalysts. Particularly, EDDS lyase shows broad non-natural substrate promiscuity and excellent enantioselectivity, allowing the selective addition of homo-and heterocycloalkyl amines (comprising four-, five-and sixmembered rings) to fumarate, giving the corresponding N-cycloalkyl-substituted l-aspartic acids with > 99% e.e. This biocatalytic methodology offers an alternative synthetic choice to prepare difficult N-cycloalkyl-substituted amino acids. Given its very broad amine scope, EDDS lyase is an exceptionally powerful synthetic tool that nicely complements the rapidly expanding toolbox of biocatalysts for asymmetric synthesis of noncanonical amino acids.

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“…The progress in this area over the past decade has been reviewed extensively. − The enantioselective hydroamination reaction catalyzed by metallocene complexes of the rare-earth elements was pioneered in the 1990s by Marks and co-workers ,− and has then been extended to nonmetallocene rare-earth-element catalysts . Parallel to this development, enantioselective catalysts based on other metals have also been reported. ,− However, there is still a great demand for catalysts that can enantioselectively transform a broad range of substrates at moderate temperatures with low catalyst loadings.…”

Section: Resultsmentioning

confidence: 99%

Enantiopure Amidinate Complexes of the Rare-Earth Elements

et al. 2016

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The synthesis of the new chiral amidine (S,S)-N,N′-bis(1-phenylethyl)pivalamidine ((S)-HPETA) and its corresponding lithium salt (S)-LiPETA are reported, and their solid-state structures were investigated by single-crystal X-ray diffraction. Depending on the stoichiometric ratio and the ion radius of the rare-earth metal, the reaction of (S)-LiPETA with anhydrous lanthanide trihalides (Ln = Sc, Y, La, Nd, Sm, Lu) afforded mono-, bis-, and tris(amidinate) complexes. The mono(amidinate) compound [{(S)-PETA}LaI 4 Li 2 (thf) 4 ], the bis(amidinate) complexes [({(S)-PETA} 2 Ln-μ-Cl) n ] (Ln = Sc, Y, Nd, Sm, Lu), and the tris(amidinate) compound [{(S)-PETA} 3 Y] were isolated and structurally characterized by single-crystal X-ray diffraction. For the bis(amidinate) compounds, either monomeric or chloro-bridged dimeric structures were observed in the solid state. Furthermore, chiral bis(amidinate)-amido and -alkyl complexes [{(S)-PETA} 2 Ln{E(SiMe 3 ) 2 }] (E = N, Ln = Y; E = CH, Ln = Sc, Y, Lu) were synthesized by salt metathesis and their catalytic activity and enantioselectivities were investigated in hydroamination/cyclization reactions. All of these compounds showed very good catalytic activity, and all of the investigated substrates were converted regiospecifically into their corresponding cyclic products under mild reaction conditions within good reaction times. The lutetium alkyl compound combined a high activity with good enantioselectivity.

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Rhodium‐Catalyzed Asymmetric Intramolecular Hydroamination of Unactivated Alkenes

Cited by 168 publications

References 65 publications

Iron-Catalyzed Reductive Coupling of Nitroarenes with Olefins: Intermediate of Iron–Nitroso Complex

Iron-Catalyzed Reductive Coupling of Nitroarenes with Olefins: Intermediate of Iron–Nitroso Complex

Biocatalytic Enantioselective Hydroaminations for Production of N‐Cycloalkyl‐Substituted L‐Aspartic Acids Using Two C−N Lyases

Enantiopure Amidinate Complexes of the Rare-Earth Elements

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