A Palladium‐Catalyzed Aminoalkynylation Strategy towards Bicyclic Heterocycles: Synthesis of (±)‐Trachelanthamidine

Nicolai, Stefano; Piemontesi, Cyril; Waser, Jérôme

doi:10.1002/anie.201100718

Cited by 178 publications

(76 citation statements)

References 66 publications

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“…19 Later it could be also extended to nitrogen nucleophiles and applied to the total synthesis of alkaloid natural products. 20 Scheme 3: Oxyalkynylation of olefins.…”

Section: First Uses Of Ebx Reagentsmentioning

confidence: 99%

Benziodoxol(on)e Reagents as Tools in Organic Synthesis: The Background behind the Discovery at the Laboratory of Catalysis and Organic Synthesis

Waser

2016

Synlett

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In this review, a personal account of our work in the field of hypervalent iodine reagents is presented. Pioneering experiments, which led to the discovery of the exceptional reactivity of EthynylBenziodoXol(on)e (EBX) reagents as electrophilic alkyne synthons is first discussed, including the alkynylation of ketoesters, olefins and heterocycles. Our further work involving EBX reagents in domino reactions and the alkynylation of thiols, as well as the use of benziodoxole reagents for azidation reactions is then described. Finally, the most recent results involving radicals and carbenes as reaction partners for EBX reagents and their first use in chemical biology are presented. The purpose of this review is not to give an extensive overview of our results, but to show the "true story" beyond the discovery by presenting the most important pioneering experiments. Failed attempts and near misses are also shortly discussed.

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“…19 Later it could be also extended to nitrogen nucleophiles and applied to the total synthesis of alkaloid natural products. 20 Scheme 3: Oxyalkynylation of olefins.…”

Section: First Uses Of Ebx Reagentsmentioning

confidence: 99%

Benziodoxol(on)e Reagents as Tools in Organic Synthesis: The Background behind the Discovery at the Laboratory of Catalysis and Organic Synthesis

Waser

2016

Synlett

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“…In this case, both aromatic and aliphatic acids could be used. In 2011, Waser and co-workers were able to extend the method to the synthesis of lactams using tosylimides as nucleophiles [151]. In this case, best results were obtained with palladium(II) chloride as catalyst in ethanol.…”

Section: Alkynylation As Part Of Domino Processesmentioning

confidence: 99%

Alkynylation with Hypervalent Iodine Reagents

Waser

2015

Topics in Current Chemistry

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Alkynes are among the most versatile functional groups in organic synthesis. They are also frequently used in chemical biology and materials science. Whereas alkynes are traditionally added as nucleophiles into organic molecules, hypervalent iodine reagents offer a unique opportunity for the development of electrophilic alkyne synthons. Since 1985, alkynyliodonium salts have been intensively used for the alkynylation of nucleophiles, in particular soft carbon nucleophiles and heteroatoms. They have made especially a strong impact in the synthesis of highly useful ynamides. Nevertheless, their use has been limited by their instability. Since 2009, more stable ethynylbenziodoxol(on)e (EBX) reagents have been discovered as superior electrophilic alkyne synthons in many transformations. They can be used for the alkynylation of acidic C-H bonds with bases or aromatic C-H bonds using transition metal catalysts. They were also highly successful for the functionalization of radicals or transition metal-catalyzed domino processes. Finally, they allowed the alkynylation of a further range of heteroatom nucleophiles, especially thiols, under exceptionally mild conditions. With these recent discoveries, hypervalent iodine reagents have definitively demonstrated their utility for the efficient synthesis of alkynes based on non-classical disconnections.

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“…Pd-каталізоване внутрішньомолекулярне амі-ноалкінілювання N-тозиламіду 198 за допомогою І(ІІІ) вмісного реагенту TIPS•EBX приводить до 6-алкінілметилпіперидинону 199 [100] (схема 83).…”

Section: синтез δ-лактонів та лактамівunclassified

Heterocyclization of amides of alkenylcarboxylic acids

Tsyzoryk¹,

Васькевич²,

Вовк³

2015

J. org. pharm. chem.

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(Ховейда, Граббса, Нолана), реакції мета-тезису, а також радикальних процесів у регіо-та стереоселективних циклізаціях амідів у м'яких умовах. Розглянуті синтетичні варіанти носять загальний характер і дозволяють поряд із процесами циклізації здійснювати спрямовану функціоналізацію O-, N-, S-вмісних малих та середніх гетероциклічних систем. HETEROCYCLIZATION OF AMIDES OF ALKENYLCARBOXYLIC ACIDS N.M.Tsyzoryk, A.I.Vaskevich, M.V.Vovk Key words: amides of alkenylcarboxylic acids; electrophilic intramolecular cyclization; lactones; lactams The latest published data on heterocyclization of amides of alkenylcarboxylic acids have been systematized. It has been proven that the electrophilic intramolecular cyclization reaction of functionally substituted olefins opened in the 70s of the last century is a convenient way of constructing different oxygen-, nitrogen-and sulfurcontaining heterocyclic compounds. It has been noted that anilides of unsaturated carboxylic acids as bifunctional nucleophilic systems containing alkenyl and aminocarbonyl functions are useful models to study the electrophilic cyclization reaction, which leads to formation of O-and N-containing heterocycles (lactones and lactams). The last of them belong to the important types of compounds used as key blocks in the synthesis of biologically active alkaloids and their analogues, pharmaceutical and agrochemical products. The effective approaches to the synthesis of new types of functionalized lactones and lactams have been developed; amides of 3-butenoic, 4-pentenoic and 5-hexenoic acids are often used as substrates for their design. Along with classical methods of synthesis of lactones and lactams the literary sources relating to the use of original catalytic electrophilic systems (Nolan, Grubbs, Hoveyda), the metathesis reaction and radical processes in regio-and stereoselective cyclization of amides under mild conditions have been analyzed and summarized in the article. The synthetic versions considered are general in nature and allow to perform the targeted functionalization of O-, N-, S-containing heterocyclic small and medium-sized systems along with the cyclization processes. ГЕТЕРОЦИКЛИЗАЦИИ АМИДОВ АЛКЕНИЛКАРБОНОВЫХ КИСЛОТ

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A Palladium‐Catalyzed Aminoalkynylation Strategy towards Bicyclic Heterocycles: Synthesis of (±)‐Trachelanthamidine

Cited by 178 publications

References 66 publications

Benziodoxol(on)e Reagents as Tools in Organic Synthesis: The Background behind the Discovery at the Laboratory of Catalysis and Organic Synthesis

Benziodoxol(on)e Reagents as Tools in Organic Synthesis: The Background behind the Discovery at the Laboratory of Catalysis and Organic Synthesis

Alkynylation with Hypervalent Iodine Reagents

Heterocyclization of amides of alkenylcarboxylic acids

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