Intermolecular Alkyl Radical Addition to Chiral <i>N</i>-Acylhydrazones Mediated by Manganese Carbonyl

Friestad, Gregory K.; Qin, Jun

doi:10.1021/ja011312k

Cited by 153 publications

(86 citation statements)

References 18 publications

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“…Starting with the butyraldehyde hydrazone, Mn-mediated photolysis with 4-chloro-iodobutane afforded the acyclic adduct in 66 % yield with a diastereomer ratio of 95:5. [46] In this case, Finkelstein conditions were needed for cyclization, and reductive removal of the auxiliary afforded coniine in 34 % overall yield for 4 steps. An interesting aspect of this reaction sequence is the direct comparison of the efficiency of radical-and carbanion-based syntheses.…”

Section: Hybrid Radical-ionic Annulationmentioning

confidence: 98%

“…This process had apparently been scarcely recognized by synthetic organic chemists prior to a series of papers by Parsons. [48] In fact, for ethyl iodide addition to 3a (Table 10), irradiation (300 nm) with [Mn 2 (CO) 10 ] using InCl 3 as a Lewis acid furnished the ethyl adduct in 85 % yield, [46] a dramatic improvement over use of triethylborane or hexamethylditin. Control experiments revealed a requirement for both irradiation and [Mn 2 (CO) 10 ].…”

Section: Manganese-mediated Radical Additionmentioning

confidence: 98%

“…[46] Presumably radical addition was followed by in situ S N 2-type cyclization. The same cyclization (giving the epimeric pyrrolidine) occurs upon ethyl addition to the 3-chlorobutyraldehyde hydrazone 24.…”

Section: Hybrid Radical-ionic Annulationmentioning

confidence: 99%

“…For example, the cleavage of a piperidine hydrazide was accomplished in this manner, with isolation of the product as the N-Boc derivative [Equation (3)]. [46] Similarly, a valerolactam-containing hydrazide was cleaved with trapping of the free amine as the acetyl derivative [Equation (4)]. [35] The oxazolidinone is not recoverable under these conditions.…”

Section: N-n Cleavage With Boranementioning

confidence: 99%

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Chiral N‐Acylhydrazones: Versatile Imino Acceptors for Asymmetric Amine Synthesis

Friestad

2005

Eur J Org Chem

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122

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Addition to C=N bonds with acyclic stereocontrol offers excellent potential for development of new carbon-carbon bond construction approaches to chiral amines. This review features the design and implementation of novel chiral Nacylhydrazones as versatile imino acceptors for addition of radicals and nucleophiles. The initial design was inspired by the goal of asymmetric radical addition to chiral C=N radical acceptors. The chiral N-acylhydrazones are prepared from commercially available materials by amination of 4-alkyl-2-oxazolidinones with NH 2 + equivalents to afford N-(amino) oxazolidinones, followed by condensation with aldehydes or ketones. These chiral N-acylhydrazones undergo addition reactions with various partners, including radicals, allylsilanes, allylindiums, silyl enol ethers, and hydride donors. The MICROREVIEWS: This feature introduces the readers to the authors' research through a concise overview of the selected topic. Reference to important work from others in the field is included.

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Section: Hybrid Radical-ionic Annulationmentioning

confidence: 98%

Section: Manganese-mediated Radical Additionmentioning

confidence: 98%

Section: Hybrid Radical-ionic Annulationmentioning

confidence: 99%

Section: N-n Cleavage With Boranementioning

confidence: 99%

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Chiral N‐Acylhydrazones: Versatile Imino Acceptors for Asymmetric Amine Synthesis

Friestad

2005

Eur J Org Chem

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122

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“…further utilized in metallate alkylation or acylation reactions. 7 -9 Recently, photochemically generated radicals from Mn 2 (CO) 10 in conjunction with alkyl halides have been successfully used in radical-based reactions such as cyclization (vi) 10,11 , coupling (vii) 12 , intermolecular addition (viii) 13 and polymerization (Scheme 2).…”

Section: Yusuf Yagci Is a Professor Of Chemistry At Istanbul Technicamentioning

confidence: 99%

Macromolecular design and application using Mn₂(CO)₁₀‐based visible light photoinitiating systems

Çiftçi

Taşdelen

Yaǧcı

2016

Polymer International

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The environmentally friendly Mn 2 (CO) 10 -based visible light photoinitiating system is a powerful method for the preparation of linear and crosslinked polymeric structures. From a practical point of view, the most important feature of this initiating system is its optical characteristics in the visible range with high quantum yield and good solubility properties. This photoinitiating system is applicable for a variety of monomers that can be polymerized via either radical or cationic mechanisms. Various complex macromolecular structures such as telechelic polymers, block and graft copolymers, polymer networks and surface modifications can be simply prepared by using halogenated precursors. This photoinitiating system is also combined with controlled radical polymerization techniques providing a mild and efficient method for polymer synthesis.

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(S)-4-Benzyl-2-oxazolidinone

Evans

Kim

Skrydstrup

et al. 2007

Encyclopedia of Reagents for Organic Synthesis

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Intermolecular Alkyl Radical Addition to Chiral N-Acylhydrazones Mediated by Manganese Carbonyl

Cited by 153 publications

References 18 publications

Chiral N‐Acylhydrazones: Versatile Imino Acceptors for Asymmetric Amine Synthesis

Chiral N‐Acylhydrazones: Versatile Imino Acceptors for Asymmetric Amine Synthesis

Macromolecular design and application using Mn₂(CO)₁₀‐based visible light photoinitiating systems

(S)-4-Benzyl-2-oxazolidinone

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Intermolecular Alkyl Radical Addition to Chiral N-Acylhydrazones Mediated by Manganese Carbonyl

Cited by 153 publications

References 18 publications

Chiral N‐Acylhydrazones: Versatile Imino Acceptors for Asymmetric Amine Synthesis

Chiral N‐Acylhydrazones: Versatile Imino Acceptors for Asymmetric Amine Synthesis

Macromolecular design and application using Mn2(CO)10‐based visible light photoinitiating systems

(S)-4-Benzyl-2-oxazolidinone

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Macromolecular design and application using Mn₂(CO)₁₀‐based visible light photoinitiating systems