Orthogonal Syntheses of 3.2.0 Bicycles from Enallenes Promoted by Visible Light

Serafino, Andrea; Balestri, Davide; Marchiò, Luciano; Malacrìa, Max; Derat, Étienne; Maestri, Giovanni

doi:10.1021/acs.orglett.0c02193

Cited by 21 publications

(22 citation statements)

References 55 publications

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“…Moreover, aliphatic 1,n-enynes 1w and 1x were also tested under standard conditions, and 1,n-allenenes 4b – e were isolated as the major products (Scheme ). Interestingly, when the obtained 1,6-allenenes ( 4b – d ) were performed in CH 2 Cl 2 at 60 °C in the absence of copper catalyst, the corresponding [2 + 2] cycloaddition bicyclo[3.2.0] products ( 3wa , 3wl , and 3wq ) were obtained in satisfactory yields, whereas 1,7-allenene 4e was mostly decomposed concomitant with partial isomerization to the corresponding alkyne 4e′ . This result excludes the transition-metal-mediated [2 + 2] cycloaddition pathways …”

Section: Resultsmentioning

confidence: 99%

Copper-Catalyzed Tandem Cross-Coupling/Thermally Promoted [2 + 2] Cycloaddition of 1,6-Enynes and Diazo Compounds To Assemble Methylenecyclobutane-Fused Ring System

et al. 2021

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An unprecedented copper-catalyzed tandem reaction of 1,6-enynes with diazo compounds via a cross-coupling/[2 + 2] cycloaddition sequence was reported. A library of methylenecyclobutane-fused ring systems including cyclobuta[b]indolines, cyclobuta[b]benzofuran, benzo[b]cyclobuta[d]thiophene, and bicyclo[3.2.0] structures were obtained in moderate to excellent yields under very mild reaction conditions. The reaction exhibited high proximal-regioselectivity and diastereoselectivity. Moreover, 1,6-allenene has proven to be the key intermediate and proceeds via a thermally promoted [2 + 2] cycloaddition in the absence of copper catalyst.

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Section: Resultsmentioning

confidence: 99%

Copper-Catalyzed Tandem Cross-Coupling/Thermally Promoted [2 + 2] Cycloaddition of 1,6-Enynes and Diazo Compounds To Assemble Methylenecyclobutane-Fused Ring System

et al. 2021

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“…Following GP-1a , product 1f was isolated (silica gel, n -hexane/EtOAc 8:2) as a white solid (328 mg, 0.95 mmol, 73%). The spectral data for this compound correspond to the literature …”

Section: Methodsmentioning

confidence: 95%

Inter/Intramolecular Cascade of 1,6-Enynes Catalyzed by All-Metal Aromatic Tripalladium Complexes and Carboxylic Acids

et al. 2021

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Trinuclear all-metal aromatic clusters are an original class of molecules with a cyclic and planar metal core. Characterized by peculiar metal–metal delocalized bonds, they represent a new frontier in transition-metal catalysis. We report a study on C–C-forming reactions of polyunsaturated substrates catalyzed by trinuclear all-metal aromatic palladium clusters. The synthesis of two new families of tricyclic compounds was obtained with a broad functional group tolerance under mild reaction conditions. A peculiar regio- and diastereoselectivity characterized the method, demonstrating that trinuclear palladium complexes are complementary to their popular mononuclear peers. Furthermore, preliminary studies on the mechanism of these polycyclization reactions revealed unique features of the homogeneous catalytic system.

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“…The following allene derivatives were prepared from the corresponding amine compounds following procedure A. The allene derivative 1q – 1v was prepared from previously reported methods …”

Section: Methodsmentioning

confidence: 99%

Ligand-Regulated Palladium-Catalyzed Regiodivergent Hydroarylation of the Distal Double Bond of Allenamides with Aryl Boronic Acid

Zhao

et al. 2021

J. Org. Chem.

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The ligand-regulated regiodivergent hydroarylation of the distal double bond of allenamides with aryl boronic acid was achieved in the presence of palladium(II) catalysts, delivering a variety of functionalized enamide with excellent E selectivity and Markovnikov/anti-Markovnikov selectivity. Two possible coordination intermediates were proposed to be responsible for the regiodivergent hydroarylation: (1) The coordination Intermediate I, which was proposed to be formed through the coordination of MeCN, distal double bond, phenyl to palladium, led to the aryl group away from the Intermediate I, inducing excellent E selectivity and anti-Markovnikov selectivity. (2) A switch of regioselectivity to 1,2-Markovnikov hydroarylation was obtained using bidentate phosphine ligand (dppf or Xantphos). The formed coordination Intermediate II led to the N-tether away from the Intermediate II and at the trans position of aryl, resulting in excellent E selectivity and Markovnikov selectivity. Meanwhile, tentative investigation on the mechanism proved that the hydron source of this hydroarylation is more likely to be boronic acid. The transmetallation between aryl boronic acid and palladium catalyst was the initial step of this transformation.

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Orthogonal Syntheses of 3.2.0 Bicycles from Enallenes Promoted by Visible Light

Cited by 21 publications

References 55 publications

Copper-Catalyzed Tandem Cross-Coupling/Thermally Promoted [2 + 2] Cycloaddition of 1,6-Enynes and Diazo Compounds To Assemble Methylenecyclobutane-Fused Ring System

Copper-Catalyzed Tandem Cross-Coupling/Thermally Promoted [2 + 2] Cycloaddition of 1,6-Enynes and Diazo Compounds To Assemble Methylenecyclobutane-Fused Ring System

Inter/Intramolecular Cascade of 1,6-Enynes Catalyzed by All-Metal Aromatic Tripalladium Complexes and Carboxylic Acids

Ligand-Regulated Palladium-Catalyzed Regiodivergent Hydroarylation of the Distal Double Bond of Allenamides with Aryl Boronic Acid

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