Transition‐Metal‐Free Deconstructive Lactamization of Piperidines

Romero‐Ibañez, Julio; Cruz‐Gregorio, Silvano; Sandoval‐Lira, Jacinto; Hernández-Pérez, Julio M.; Quintero, Leticia; Sartillo‐Piscil, Fernando

doi:10.1002/anie.201903880

Cited by 23 publications

(19 citation statements)

References 48 publications

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“…Good yields of 3-alkyl-, 3-aryl-, 3-ester-, and 3-ether-substituted 2-pyrrolidinones 68a-e were obtained from their corresponding 4-substituted piperidines (Scheme 18c). 42…”

Section: Account Synlett 7 Deconstructive Lactamization Of Piperidinesmentioning

confidence: 99%

“…Good yields of 3-alkyl-, 3-aryl-, 3-ester-, and 3-ether-substituted 2-pyrrolidinones 68a-e were obtained from their corresponding 4-substituted piperidines (Scheme 18c). 42 Scheme 18 (a) Silver-mediated deconstructive dehomologation of piperidines developed by Sarpong, (b) transition-metal-free deconstructive lactamization of piperidines, (c) cope of deconstructive lactamization of piperidines This new methodology to access -lactams from piperidines allowed us to construct important precursors of biological active compounds like (+)-harmicine and 4-hydroxypyrrolidinones (S)-69. (+)-Harmicine was prepared from piperidine 70 which was subjected to a deconstructive functionalization to pyrrolidinone 71.…”

Section: Account Synlett 7 Deconstructive Lactamization Of Piperidinesmentioning

confidence: 99%

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Transition-Metal-Free Functionalization of Saturated and Unsaturated Amines to Bioactive Alkaloids Mediated by Sodium Chlorite

Romero‐Ibañez¹,

Fuentes²,

Sartillo‐Piscil³

2020

Synlett

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New approaches to the synthesis of alkaloids through the straightforward functionalization of C(sp3)–H and C(sp2)=C(sp2) bonds of simple five and six-membered ring N-heterocycles are highlighted. The direct functionalization of preexisting N-heterocycles to advanced alkaloids intermediates is a chemical operation that commonly requires the intervention of transition or precious metals. Regardless the inherent unwanted waste production, the high economical cost of many transition metal catalysts limits their use globally. Here, we account our efforts directed toward the synthesis of bioactive alkaloids under an economic and ecological fashion by using NaClO2 as the key activating or oxidizing reagent that substitutes the use of transition metal catalysts. While undesired metal wastes are collected during the extraction process of a transition metal catalyzed reaction, innocuous NaCl is the commonly product waste when NaClO2 is employed in our chemical transformations. Beginning with the synthesis of 2,3-epoxyamides from allyl amines, we concluded with the functionalization of multiple and remote C(sp3)-H and C(sp3)–C(sp3) bonds in piperidine rings that enabled the preparation of important bioactive alkaloids. For the latter functionalization, a precise amount of co-oxidant reagent (NaOCl) and radical 2,2,6,6-tetramethylpiperidinyloxy (TEMPO) were needed.

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“…Good yields of 3-alkyl-, 3-aryl-, 3-ester-, and 3-ether-substituted 2-pyrrolidinones 68a-e were obtained from their corresponding 4-substituted piperidines (Scheme 18c). 42…”

Section: Account Synlett 7 Deconstructive Lactamization Of Piperidinesmentioning

confidence: 99%

Section: Account Synlett 7 Deconstructive Lactamization Of Piperidinesmentioning

confidence: 99%

Transition-Metal-Free Functionalization of Saturated and Unsaturated Amines to Bioactive Alkaloids Mediated by Sodium Chlorite

Romero‐Ibañez¹,

Fuentes²,

Sartillo‐Piscil³

2020

Synlett

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“…Deconstructive functionalizations enabling the selective cleavage of carbon–carbon σ-bonds of unreactive cyclic hydrocarbons have become the focus of recent intense research efforts and also constitute a much more challenging task in organic community, probably due to the low polarity and high bond-dissociation energy (BDE) of unactivated carbon–carbon single bonds . Specifically, redox-active cyclic oximes could serve as cyanoalkyl radical precursors through deconstructive processes .…”

Section: Introductionmentioning

confidence: 99%

Cyclic Oxime Esters as Deconstructive Bifunctional Reagents for Cyanoalkyl Esterification of 1,6-Enynes

et al. 2021

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A concise copper catalysis strategy for the addition−cyclization of cyclic oxime esters across 1,6-enynes with high stereoselectivity to generate 1-indanones bearing an allcarbon quaternary center is reported. In this process, singleelectron reduction of cyclic oxime esters enables deconstructive carbon−carbon cleavage to provide a key cyanopropyl radical poised for the addition−cyclization. This reaction is redox-neutral, exhibits good functional group compatibility, and features 100% atomic utilization. This process driven by copper catalyst makes readily available cyclic oxime esters as bifunctional reagents to demonstrate convergent synthesis.

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“…Despite recent advances in the realm of C-C bond transformations [17][18][19][20] , the selective cleavage of C-N bonds would be a compelling strategy for ring-opening functionalization of cyclic amines. Nonetheless, the process that cleaves and turns C-N bonds into versatile functionalities is still relatively scarce.…”

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confidence: 99%

Ring-opening functionalizations of unstrained cyclic amines enabled by difluorocarbene transfer

et al. 2020

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Chemical synthesis based on the skeletal variation has been prolifically utilized as an attractive approach for modification of molecular properties. Given the ubiquity of unstrained cyclic amines, the ability to directly alter such motifs would grant an efficient platform to access unique chemical space. Here, we report a highly efficient and practical strategy that enables the selective ring-opening functionalization of unstrained cyclic amines. The use of difluorocarbene leads to a wide variety of multifaceted acyclic architectures, which can be further diversified to a range of distinctive homologative cyclic scaffolds. The virtue of this deconstructive strategy is demonstrated by successful modification of several natural products and pharmaceutical analogues.

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Transition‐Metal‐Free Deconstructive Lactamization of Piperidines

Cited by 23 publications

References 48 publications

Transition-Metal-Free Functionalization of Saturated and Unsaturated Amines to Bioactive Alkaloids Mediated by Sodium Chlorite

Transition-Metal-Free Functionalization of Saturated and Unsaturated Amines to Bioactive Alkaloids Mediated by Sodium Chlorite

Cyclic Oxime Esters as Deconstructive Bifunctional Reagents for Cyanoalkyl Esterification of 1,6-Enynes

Ring-opening functionalizations of unstrained cyclic amines enabled by difluorocarbene transfer

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