Primary α-tertiary amine synthesis via α-C–H functionalization DOI Creative Commons
Dhananjayan Vasu, Ángel L. Fuentes de Arriba, Jamie A. Leitch

и другие.

Chemical Science, Год журнала: 2019, Номер 10(11), С. 3401 - 3407

Опубликована: Янв. 1, 2019

A quinone-mediated general synthetic platform for the construction of primary α-tertiary amines from abundant α-branched amine starting materials is described. This procedure pivots on efficient in situ generation reactive ketimine intermediates and subsequent reaction with carbon-centered nucleophiles such as organomagnesium organolithium reagents, TMSCN, creating quaternary centers. Furthermore, extension to reverse polarity photoredox catalysis enables reactivity electrophiles, via a nucleophilic α-amino radical intermediate. efficient, broadly applicable scalable amine-to-amine was successfully applied library API synthesis functionalization drug molecules.

Язык: Английский

Regioselective Alkylative Cross-Coupling of Remote Unactivated C(sp3)–H Bonds DOI

Scott M. Thullen,

Sean M. Treacy, Tomislav Rovis

и другие.

Journal of the American Chemical Society, Год журнала: 2019, Номер 141(36), С. 14062 - 14067

Опубликована: Сен. 3, 2019

The functionalization of unactivated C(sp3)-H bonds poses a significant challenge due to their ubiquity and relative similarity in most organic frameworks. Herein, we describe the use combined photoredox nickel catalytic system for regioselective C(sp3)-C(sp3) coupling alkyl bromides. Positional selectivity is dictated by 1,5-hydrogen atom transfer (HAT) reaction pendent amide. Interception this radical Ni catalyst allows distal alkylation occur good yield excellent selectivity.

Язык: Английский

Процитировано

89

Practical, metal-free remote heteroarylation of amides via unactivated C(sp3)–H bond functionalization DOI Creative Commons
Nana Tang, Xinxin Wu, Chen Zhu

и другие.

Chemical Science, Год журнала: 2019, Номер 10(28), С. 6915 - 6919

Опубликована: Янв. 1, 2019

A simple and practical approach for the regioselective heteroarylation of amides via unactivated C(sp3)–H bond functionalization is described.

Язык: Английский

Процитировано

83

Functionalization of remote C(sp3)-H bonds enabled by copper-catalyzed coupling of O-acyloximes with terminal alkynes DOI Creative Commons

Zhaodong Li,

Rubén O. Torres‐Ochoa, Qian Wang

и другие.

Nature Communications, Год журнала: 2020, Номер 11(1)

Опубликована: Янв. 21, 2020

Abstract Transition metal catalyzed Sonogashira cross-coupling of terminal alkynes with aryl(vinyl) (pseudo)halides has been successfully extended to alkyl halides for the synthesis functionalized internal alkynes. The direct alkynylation remote unfunctionalized sp 3 carbon by remains difficult realize. We report herein an approach this synthetic challenge developing two catalytic protocols. In presence a amount Cu(I) salt and tridentate ligand ( t Bu -terpyridine), O -acyloximes derived from cycloalkanones acyclic ketones are efficiently coupled afford variety γ- δ-alkynyl nitriles γ-alkynyl ketones, respectively. These reactions proceed through domino sequence involving copper-catalyzed reductive generation iminyl radical followed translocation via either β-scission or 1,5-hydrogen atom transfer (1,5-HAT) resulting translocated radicals. protocols applicable complex natural products.

Язык: Английский

Процитировано

82

Copper‐Catalyzed N−F Bond Activation for Uniform Intramolecular C−H Amination Yielding Pyrrolidines and Piperidines DOI
Daniel Bafaluy, José María Muñoz‐Molina,

Ignacio Funes‐Ardoiz

и другие.

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(26), С. 8912 - 8916

Опубликована: Апрель 18, 2019

The dual function of the N-F bond as an effective oxidant and subsequent nitrogen source in intramolecular aliphatic C-H functionalization reactions is explored. Copper catalysis demonstrated to exercise full regio- chemoselectivity control, which opens new synthetic avenues nitrogenated heterocycles with predictable ring sizes. For first time, a uniform manifold has been identified for construction both pyrrolidine piperidine cores. individual steps this copper oxidation were elucidated by control experiments computational studies, clarifying singularity characterizing catalytic cycle be based on copper(I/II) manifold.

Язык: Английский

Процитировано

81

Primary α-tertiary amine synthesis via α-C–H functionalization DOI Creative Commons
Dhananjayan Vasu, Ángel L. Fuentes de Arriba, Jamie A. Leitch

и другие.

Chemical Science, Год журнала: 2019, Номер 10(11), С. 3401 - 3407

Опубликована: Янв. 1, 2019

A quinone-mediated general synthetic platform for the construction of primary α-tertiary amines from abundant α-branched amine starting materials is described. This procedure pivots on efficient in situ generation reactive ketimine intermediates and subsequent reaction with carbon-centered nucleophiles such as organomagnesium organolithium reagents, TMSCN, creating quaternary centers. Furthermore, extension to reverse polarity photoredox catalysis enables reactivity electrophiles, via a nucleophilic α-amino radical intermediate. efficient, broadly applicable scalable amine-to-amine was successfully applied library API synthesis functionalization drug molecules.

Язык: Английский

Процитировано

77