Radical‐Mediated Alkenylation, Alkynylation, Methanimination, and Cyanation of <i>B</i>‐Alkylcatecholboranes

Schaffner, Arnaud‐Pierre; Darmency, Vincent; Renaud, Philippe

doi:10.1002/anie.200601206

Cited by 145 publications

(67 citation statements)

References 44 publications

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“…Metal-mediated methods have been limited to the use of alkynyl bromides [143], whereas radical approaches have been dominated by alkynyl sulfones [21][22]. Nevertheless, Yu and Chen and co-workers reported recently that aromatic EBX reagents were highly efficient for the interception of radical generated in -position to heteroatoms [144].…”

Section: Alkynylation Of Aliphatic C-h Bondsmentioning

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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Section: Alkynylation Of Aliphatic C-h Bondsmentioning

confidence: 99%

Alkynylation with Hypervalent Iodine Reagents

Waser

2015

Topics in Current Chemistry

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“…80 More recently, Renaud and co-workers reported the radical alkynylation of β-alkylcatecholboranes (Scheme 68). 84 Phenylsulfones were used instead of triflones. This reaction was limited to acetylenes bearing groups able to stabilize a radical at their α position, such as phenyl or trimethylsilyl.…”

Section: Scheme 67mentioning

confidence: 99%

Electrophilic alkynylation: the dark side of acetylene chemistry

2012

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In addition to the well-established nucleophilic alkynylation, the use of electrophilic alkynes can expand 5 tremendously the scope of acetylene transfer reactions. The use of metal catalysis has recently led to a rebirth of this research area. Halogenoalkynes, hypervalent alkynyliodoniums, acetylene sulfones and in situ oxidation of terminal acetylenes are the most often used for electrophilic alkynylation. Heteroatoms such as N, O, S and P can be now efficiently alkynylated. For C-C bond formation, electrophilic acetylenes can be coupled with different organometallics reagents. Recently, the first breakthrough in 10 direct C-H and C=C bond alkynylation have also been reported. Finally, sulfonyl acetylenes are efficient for alkyne transfer on carbon-centered radicals.

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“…2006 wurde über eine radikalische deborierende Alkinylierung von B-Alkylcatecholboranen mit Alkinylsulfonen durch Di-tert-butylhyponitrit als Radikalinitiator berichtet. [8] Kürzlich wurden mit Ethinylbenziodoxolonen (EBX) als radikalische Alkinylierungsreagentien eine silberkatalysierte oxidative decarboxylierende Alkinylierung von aliphatischen Carbonsäuren [9] und durch sichtbares Licht induzierte deborierende Alkinylierung von Alkyltrifluorboraten erreicht. [10] Die große Anwendungsbreite ist ein weiterer Vorteil der radikalischen C(sp 3 )-C(sp)-Kupplungen -aber die meisten dieser Methoden beruhen auf gefährlichen Radikalinitiatoren oder externen Oxidationsmitteln (Organostannane,I od(III)-Reagentien, AIBN,K 2 S 2 O 8 usw.)…”

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Eine hocheffiziente Gold‐katalysierte Photoredox‐α‐C(sp³)‐H‐ Alkinylierung von tertiären aliphatischen Aminen durch Sonnenlicht

et al. 2015

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Eine neue a-C(sp 3 )-H-Alkinylierung nichtaktivierter tertiärer aliphatischer Amine mit 1-Iodalkinen als radikalischeA lkinylierungsreagentien in Gegenwart von [Au 2 (mdppm) 2 ] 2+ im Sonnenlicht liefert Propargylamine.B asierend auf mechanistischen Studien zur C(sp 3 )-C(sp)-Bindungsknüpfung wird eine C-C-Kupplung eines a-Aminoalkylradikals und eines Alkinylradikals vorgeschlagen. Die milden, einfachen, effizienten und hochselektiven C(sp 3 )-H-Alkinylierungen zeigen eine exzellente Regioselektivität und eine gute Toleranz gegenüber funktionellen Gruppen. Gramm-Mengen konnten mit Sonnenlichta ls saubere und nachhaltige Energiequelle umgesetzt werden.

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Radical‐Mediated Alkenylation, Alkynylation, Methanimination, and Cyanation of B‐Alkylcatecholboranes

Abstract: Radical connection: Organoboranes, prepared in situ from hydroboration of olefins with catecholborane, undergo efficient coupling reactions with vinyl and alkynyl sulfones through a radical mechanism. This procedure was also extended to the acylation and cyanation of organoboranes.

Cited by 145 publications

References 44 publications

Alkynylation with Hypervalent Iodine Reagents

Alkynylation with Hypervalent Iodine Reagents

Electrophilic alkynylation: the dark side of acetylene chemistry

Eine hocheffiziente Gold‐katalysierte Photoredox‐α‐C(sp³)‐H‐ Alkinylierung von tertiären aliphatischen Aminen durch Sonnenlicht

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Radical‐Mediated Alkenylation, Alkynylation, Methanimination, and Cyanation of B‐Alkylcatecholboranes

Abstract: Radical connection: Organoboranes, prepared in situ from hydroboration of olefins with catecholborane, undergo efficient coupling reactions with vinyl and alkynyl sulfones through a radical mechanism. This procedure was also extended to the acylation and cyanation of organoboranes.

Cited by 145 publications

References 44 publications

Alkynylation with Hypervalent Iodine Reagents

Alkynylation with Hypervalent Iodine Reagents

Electrophilic alkynylation: the dark side of acetylene chemistry

Eine hocheffiziente Gold‐katalysierte Photoredox‐α‐C(sp3)‐H‐ Alkinylierung von tertiären aliphatischen Aminen durch Sonnenlicht

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About

Eine hocheffiziente Gold‐katalysierte Photoredox‐α‐C(sp³)‐H‐ Alkinylierung von tertiären aliphatischen Aminen durch Sonnenlicht