An Efficient Generation of a Functionalized Tertiary-Alkyl Radical for Copper-catalyzed Tertiary-Alkylative Mizoroki-Heck type Reaction

Noji, Takashi; Noda, Yujiro; Fujimoto, Ryo; Sakashita, Tomomi

doi:10.1021/ja409661n

Cited by 205 publications

(75 citation statements)

References 37 publications

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“…In contrast, alkyl-Heck-type reactions were much more challenging and rarely explored until the last decade. Pioneered by Oshima 26 and Fu's seminal works 27 , effective strategies have been developed to facilitate this alkenylations with simple alkyl halides as electrophiles [28][29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44] . Notably, two elegant palladium-catalyzed cases involving alkyl C-H activation were disclosed by the groups of Yu 45 and Sanford 46 , which employed N-arylamide or pyridine as a neighboring directing group with stoichiometric amounts of external oxidant.…”

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confidence: 99%

Direct dehydrogenative alkyl Heck-couplings of vinylarenes with umpolung aldehydes catalyzed by nickel

Zhu

2019

Nat Commun

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Alkenes are fundamental functionalities in nature and highly useful intermediates in organic synthesis, medicinal chemistry and material sciences. Transition-metal-catalyzed Heck couplings with organic halides as electrophiles have been established as a powerful protocol for the synthesis of this valuable building block. However, the requirement of organic halides and the generation of stoichiometric hazardous halide wastes may cause significant sustainable concerns. The halide-free oxidative Heck alkenylations involving organometallics or arenes as the coupling partners provide a facile and alternative pathway. Nonetheless, stoichiometric amounts of extra oxidant are essential in most cases. Herein, we present a direct dehydrogenative alkyl Heck-coupling reaction under oxidant-free conditions, liberating hydrogen, nitrogen and water as the side products. Excellent regioselectivity is achieved via neighboring oxygen atom coordination. Broad substrate scope, great functional group (ketone, ester, phenol, free amine, amide etc) tolerance and modification of pharmaceutical candidates and biological molecules exemplified its generality and practicability.

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confidence: 99%

Direct dehydrogenative alkyl Heck-couplings of vinylarenes with umpolung aldehydes catalyzed by nickel

Zhu

2019

Nat Commun

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“…Importantly, we show herein expansion of the method to involve intermolecular C-C bond formation via alkyl Heck-type couplings with vinyl arenes (Scheme 1). [13b,20] This method is complementary in substrate scope to existing catalytic enantioselective carboetherifications [15–18,21–23] as aliphatic alcohols with unactivated terminal alkenes are excellent substrates, and various vinylarenes undergo coupling with them (vide infra).…”

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Enantioselective Copper‐Catalyzed Carboetherification of Unactivated Alkenes

et al. 2014

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Chiral saturated oxygen heterocycles are important components of bioactive compounds. Cyclization of alcohols onto pendant alkenes is a direct route to their synthesis, but few catalytic enantioselective methods enabling cyclization onto unactivated alkenes exist. Herein is reported a highly efficient copper-catalyzed cyclization of γ-unsaturated pentenols that terminates in C-C bond formation, a net alkene carboetherification. Both intra- and intermolecular C-C bond formations are demonstrated, yielding functionalized chiral tetrahydrofurans as well as fused-ring and bridged-ring oxabicyclic products. Transition state calculations support a cis-oxycupration stereochemistry-determining step.

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“…Ac opper-triamine catalyzed tertiarya lkylative M-H reaction of styrenes with functionalized tertiarya lkyl halidest og ive the corresponding tertiarya lkylated styrenes in good yields has been described (Scheme 42). [39] Notably,s ubstrates with electron-withdrawing groups were also suitable under these conditions. The formation of tertiarya lkyl radicals pecies is the key step in this transformation.…”

Section: Heck-type Couplingmentioning

confidence: 99%

Developments in the Chemistry of α‐Carbonyl Alkyl Bromides

Ouyang

Song

2018

Chemistry An Asian Journal

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α-Carbonyl alkyl bromides are powerful reactive species for the formation of carbon-carbon bonds. Strategies relying on intermolecular C-H functionalization and cross-coupling reactions, also referred to as intramolecular cyclization, have been employed for the construction of alkenes, alkanes, ketones, and other natural-product-like ring compounds from simple alkynes, alkenes, and 1,n-enynes. In view of the importance of these α-carbonyl alkyl bromides, especially the difluoro carbonyl alkyl bromides, many researchers have focused their efforts to develop facile and mild synthetic methods for compounds with important biological activities. This review aims to briefly discuss the latest developments in the transformation of α-carbonyl alkyl bromides with emphasis on the related reaction mechanisms.

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An Efficient Generation of a Functionalized Tertiary-Alkyl Radical for Copper-catalyzed Tertiary-Alkylative Mizoroki-Heck type Reaction

Cited by 205 publications

References 37 publications

Direct dehydrogenative alkyl Heck-couplings of vinylarenes with umpolung aldehydes catalyzed by nickel

Direct dehydrogenative alkyl Heck-couplings of vinylarenes with umpolung aldehydes catalyzed by nickel

Enantioselective Copper‐Catalyzed Carboetherification of Unactivated Alkenes

Developments in the Chemistry of α‐Carbonyl Alkyl Bromides

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