Determining the scope of the lanthanide mediated, sequential hydroamination/C–C cyclization reaction: formation of tricyclic and tetracyclic aromatic nitrogen heterocycles

Molander, Gary A.; Pack, Shawn K.

doi:10.1016/j.tet.2003.08.071

Cited by 39 publications

(25 citation statements)

References 14 publications

(18 reference statements)

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“…1-25 Methods that provide for concise build-up of functionality by installing two rings in a single operation may prove especially useful in the concise synthesis of nitrogen heterocycles for natural product synthesis and drug discovery endeavors. 11,14,15,[26][27][28][29][30][31][32] Herein is reported an expansion of the substrate scope of the copper(II) promoted intramolecular carboamination of unactivated alkenes, 11 a transformation that installs two new rings from acyclic N-substituted amines. demonstrated a preference (ca.…”

Section: Introductionmentioning

confidence: 99%

Pyrrolidine and Piperidine Formation via Copper(II) Carboxylate-Promoted Intramolecular Carboamination of Unactivated Olefins: Diastereoselectivity and Mechanism

et al. 2007

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An expanded substrate scope and in-depth analysis of the reaction mechanism of the copper(II) carboxylate-promoted intramolecular carboamination of unactivated alkenes is described. This method provides access to N-functionalized pyrrolidines and piperidines. Both aromatic and aliphatic gamma- and delta-alkenyl N-arylsulfonamides undergo the oxidative cyclization reaction efficiently. N-Benzoyl-2-allylaniline also underwent the oxidative cyclization. The terminal olefin substrates examined were more reactive than those with internal olefins, and the latter terminated in elimination rather than carbon-carbon bond formation. The efficiency of the reaction was enhanced by the use of more organic soluble copper(II) carboxylate salts, copper(II) neodecanoate in particular. The reaction times were reduced by the use of microwave heating. High levels of diastereoselectivity were observed in the synthesis of 2,5-disubstituted pyrrolidines, wherein the cis substitution pattern predominates. The mechanism of the reaction is discussed in the context of the observed reactivity and in comparison to analogous reactions promoted by other reagents and conditions. Our evidence supports a mechanism wherein the N-C bond is formed via intramolecular syn aminocupration and the C-C bond is formed via intramolecular addition of a primary carbon radical to an aromatic ring.

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Section: Introductionmentioning

confidence: 99%

Pyrrolidine and Piperidine Formation via Copper(II) Carboxylate-Promoted Intramolecular Carboamination of Unactivated Olefins: Diastereoselectivity and Mechanism

et al. 2007

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“…The importance of the nitrile group in the side chain of the BP opens the way to the possibility to reduce this moiety to the corresponding amino group, that could further react to give substituted N‐BPs. Several examples of cyano group reduction are reported in the literature using different reducing agents such as hydrogen, sodium borohydride, lithium aluminum hydride, or others . Reduction attempts and functionalization of nitrile group will be the subject of future studies in order to obtain a new class of γ ‐amino BPs as potential new N‐BPs.…”

Section: Discussionmentioning

confidence: 99%

Nitrile Containing Bisphosphonates: Easy Synthesis through Metal Catalyzed Michael Addition

et al. 2017

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New nitrile‐containing gem‐bisphosphonates as drug candidates for the contrast of osteoporosis are presented, their synthesis being based on the metal catalyzed Michael conjugate addition of trimethylsilyl cyanide to unsaturated bisphosphonate precursors. Zn(OTf)2 turned out to be the most efficient metal catalyst for the reaction enabling the formation of β‐nitrile substituted bisphosphonates in good yields. The corresponding final bisphosphonic acids bearing the nitrile moiety were obtained by deprotection of the ethyl ester moiety. They showed aggregation properties in water due to their amphiphilic nature and will be evaluated in order to assess their biological anti‐osteoclast activity.

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“…Exposure to NaH in DMF smoothly exchanged three functional groups on 12 yielding aminophenol 13 , which was then converted to PMP acetal 14 after reduction of the aldehyde. Conversion to the unstable benzyl chloride 15 proceeds smoothly using well‐established conditions with methyl chloroformate and potassium carbonate …”

Section: Methodsmentioning

confidence: 99%

“…Conversion to the unstable benzylc hloride 15 proceeds smoothly using well-established conditions with methyl chloroformatea nd potassium carbonate. [16] The benzylic chloride 15 was found to be very prone to decomposition in solution,p articularly upon heating. To circumvent this challenge and activate the benzylic chloride for nucleophilic attack on the TBS-protected Weinreib amide of (S)lactic acid,w es elected at ellurium-mediated process, [17] which yielded 16 in 84 %y ield (Scheme 5).…”

mentioning

confidence: 99%

Generation of Benzyne Species from Diphenylphosphoryl Derivatives: Simultaneous Exchange of Three Functional Groups

Gorobets

Parvez

Derksen

et al. 2016

Chemistry A European J

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Interaction of (2-diphenylphosphoryl-3-iodo-4-methoxy-phenyl) methanol with NaH in DMF at ambient temperature results in the generation of benzyne intermediates that can be trapped by furan or DMF. Trapping with DMF forms 3-(dimethylaminomethyl)-2-hydroxy-6-methoxybenzaldehyde demonstrating the simultaneous exchange of three functionalities in a single step. The presence of the alkoxy substituent adjacent to iodine is critical for high regioselectivity addition of DMF. The corresponding bromide or triflate can be used in place of the iodide with equal efficiency. This methodology was used to synthesize the reported structure of gigasol and leading to a structural reassignment of this biscoumarin natural product.

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Determining the scope of the lanthanide mediated, sequential hydroamination/C–C cyclization reaction: formation of tricyclic and tetracyclic aromatic nitrogen heterocycles

Cited by 39 publications

References 14 publications

Pyrrolidine and Piperidine Formation via Copper(II) Carboxylate-Promoted Intramolecular Carboamination of Unactivated Olefins: Diastereoselectivity and Mechanism

Pyrrolidine and Piperidine Formation via Copper(II) Carboxylate-Promoted Intramolecular Carboamination of Unactivated Olefins: Diastereoselectivity and Mechanism

Nitrile Containing Bisphosphonates: Easy Synthesis through Metal Catalyzed Michael Addition

Generation of Benzyne Species from Diphenylphosphoryl Derivatives: Simultaneous Exchange of Three Functional Groups

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