Domino Synthesis of α,β‐Unsaturated γ‐Lactams by Stereoselective Amination of α‐Tertiary Allylic Alcohols

Xie, Jia‐Ning; Xue, Sijing; Escudero‐Adán, Eduardo C.; Kleij, Arjan W.

doi:10.1002/ange.201810160

Angewandte Chemie

2018

DOI: 10.1002/ange.201810160

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Domino Synthesis of α,β‐Unsaturated γ‐Lactams by Stereoselective Amination of α‐Tertiary Allylic Alcohols

Jia‐Ning Xie

Sijing Xue

Eduardo C. Escudero‐Adán

et al.

Abstract: Tertiary allylic alcohols equipped with ac arboxyl group can be smoothly aminated under ambient conditions by ac onceptually new and stereoselective protocol under palladium catalysis.The in situ formed Z-configured g-amino acid cyclizes to affordana,b-unsaturated g-lactam, releasing water as the only byproduct. This practical catalytic transformation highlights the use of ac arboxyl group acting as an activating and stereodirecting functional group to provide awide series of pharma-relevant building blocks.V … Show more

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Cited by 6 publications

References 79 publications

(41 reference statements)

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Visible‐Light‐Induced Photoredox 1,1‐Dichloromethylation of Alkenes with Chloroform

Cheng

Chen

et al. 2022

Adv Synth Catal

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A photoredox 1,1‐dichloromethylation of alkenes with the readily available bulk chemical chloroform was described, furnishing a variety of 1,1‐dichloroalkane products selectively. Furthermore, this transformation could proceed smoothly on gram‐scale, and the obtained products could transform into diverse γ‐lactam derivatives with simple treatment. Mechanistically, the single electron transfer (SET) with excited photocatalyst and subsequent deprotonation of triethylamine generates the key α‐aminoradical intermediate, which enables selective Cl‐atom transfer of chloroform. The specific selectivity, broad substrate scope, as well as the mild reaction conditions make this strategy especially attractive.

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Visible‐Light‐Induced Photoredox 1,1‐Dichloromethylation of Alkenes with Chloroform

Cheng

Chen

et al. 2022

Adv Synth Catal

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Regioselective Nitrosocarbonyl Aldol Reaction of Deconjugated Butyrolactams: Synthesis of γ‐Heterosubstituted α,β‐Unsaturated γ‐Lactams

2021

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The nitrosocarbonyl aldol reaction of deconjugated butyrolactams is developed employing quinidine as organocatalyst. The nitrosocarbonyl species generated in situ from hydroxamic acids react with a variety of deconjugated butyrolactams at room temperature, offering valuable α,β-unsaturated γ-lactams bearing heterosubstituted quaternary carbon center in very high yields. This nitrosocarbonyl aldol reaction is O-selective and proceeds exclusively at the γ-center of deconjugated butyrolactams. The reaction is scalable, accommodates diverse functional groups, and is also effective with azodicarboxylates.γ-Lactams and derivatives thereof, particularly those encompass unsaturation in the ring framework and quaternary carbon center at the γ-position, constitute an important class of heterocycles with eminence in medicinal and pharmaceutical chemistry. [1,2] They represent the core structure of many natural products and biologically significant molecules (Figure 1). [2] They are also widely used as versatile building blocks in organic synthesis towards complex targets. [3] Consequently, devising straightforward strategies to access functionally rich unsaturated γ-lactams remains in the limelight of organic synthesis. [4] In this scenario, among the diverse synthetic endeavours, exploration of nucleophilic reactivity of γ-monosubstituted deconjugated butyrolactams have fetched considerable impetus as they are accessible in diverse substitution patterns from readily available precursors. [5] However, this strategy results in dienolate intermediate which could react with electrophile either through the αor γ-position, leading to a mixture of regioisomeric products (Scheme 1a). Further, such reactivity of deconjugated butyrolactams has majorly been investigated for carbon-carbon bond forming reactions and exploration in carbon-heteroatom bond forming reactions are scarce. In 2017, Mukherjee et al. reported sulfenylation and selenylation of γ-monosubstituted deconjugated butyrolac-[a

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Silver‐Mediated Cascade Synthesis of Functionalized 1,4‐Dihydro‐2H‐benzo‐1,3‐oxazin‐2‐ones from Carbon Dioxide

Benet‐Buchholz

Escudero‐Adán

et al. 2023

Angewandte Chemie

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A conceptually novel catalytic domino approach is presented for the synthesis of highly functional 1,4‐dihydro‐2H‐1,3‐benzoxazine‐2‐one derivatives. Key to the chemoselectivity is a proper design of the precursor to override thermodynamically favored parasitic cyclization processes and empower the formation of the desired product through Thorpe–Ingold effects. The synthetic diversity of these CO2‐based heterocycles is further demonstrated, and the isolation of a reaction intermediate supports an unusual ring‐expansion sequence from an α‐alkylidene, five‐membered cyclic carbonate to a six‐membered cyclic carbamate by N‐induced isomerization.

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Domino Synthesis of α,β‐Unsaturated γ‐Lactams by Stereoselective Amination of α‐Tertiary Allylic Alcohols

Cited by 6 publications

References 79 publications

Visible‐Light‐Induced Photoredox 1,1‐Dichloromethylation of Alkenes with Chloroform

Visible‐Light‐Induced Photoredox 1,1‐Dichloromethylation of Alkenes with Chloroform

Regioselective Nitrosocarbonyl Aldol Reaction of Deconjugated Butyrolactams: Synthesis of γ‐Heterosubstituted α,β‐Unsaturated γ‐Lactams

Silver‐Mediated Cascade Synthesis of Functionalized 1,4‐Dihydro‐2H‐benzo‐1,3‐oxazin‐2‐ones from Carbon Dioxide

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