Generation and Trapping of Cyclopentenylidene Gold Species: Four Pathways to Polycyclic Compounds

Lemière, Gilles; Gandon, Vincent; Cariou, Kevin; Hours, Alexandra; Fukuyama, Takahide; Dhimane, Anne‐Lise; Fensterbank, Louis; Malacrìa, Max

doi:10.1021/ja808872u

Cited by 226 publications

(96 citation statements)

References 150 publications

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“…[21] The intermediate cyclopropyl endo-gold carbenes can be trapped to form biscyclopropane derivatives, which is in agreement with cyclopropanations observed in gold(I)-catalyzed cyclization of vinyl allenes, which proceed through similar intermediates. [29] According to DFT calculation, this intramolecular cyclopropanation from 1,5-enynes proceeds by a concerted process similar to that found before for the Scheme 9. Comparison between the intramolecular arylation of 1,5-enynes (9) with that of 1,6-enynes (28).…”

Section: Resultssupporting

confidence: 66%

Nature of the Intermediates in Gold(I)‐Catalyzed Cyclizations of 1,5‐Enynes

López‐Carrillo

Huguet

Mosquera

et al. 2011

Chemistry A European J

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The carbene or carbocationic nature of the intermediates in the gold-catalyzed cycloisomerization of 1,5-enynes can be revealed, depending on the ligands on the gold catalysts. Gold complexes with highly electron-donating ligands promote reactions that proceed via intermediates with carbene-like character, leading to products with a bicyclo[3.1.0]hexene skeleton. The intermediate cyclopropyl endo-gold carbenes formed in this cyclization have been trapped, for the first time, to give biscyclopropane derivatives in a reaction that proceeds in a concerted fashion, according to DFT calculations.

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Section: Resultssupporting

confidence: 66%

Nature of the Intermediates in Gold(I)‐Catalyzed Cyclizations of 1,5‐Enynes

López‐Carrillo

Huguet

Mosquera

et al. 2011

Chemistry A European J

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“…74 This intermediate can further react by intramolecular cyclopropanation to form tricyclic structure 39 .…”

Section: Evolution Of the Key Gold Intermediatesmentioning

confidence: 99%

Intriguing mechanistic labyrinths in gold(i) catalysis

2014

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“…At this point, we decided to turn towards triisopropylsilyl acetylenes derivatives, which had demonstrated exceptional properties in metal catalysis. 11,13 Gratifyingly, whereas chloroacetylene 5d displayed only low conversion (entry 4) and iodoacetylene 5e lead to dimerization (entry 5), 14 a promising 69% of yield was obtained using 2 mol% Pd2(dba)3 and DPE-Phos as ligand with bromoacetylene 5a (entry 6).…”

Section: Scheme 1 Oxy-and Amino Alkynylation Of Alkenesmentioning

confidence: 99%

Pd(0)-Catalyzed Oxy- and Aminoalkynylation of Olefins for the Synthesis of Tetrahydrofurans and Pyrrolidines

Nicolai

Waser

2011

Org. Lett.

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The first Pd(0)-catalyzed intramolecular oxy-and amino-alkynylation of non-activated olefins is reported. The reaction gives access to important tetrahydrofuran and pyrrolidine heterocycles with high diastereoselectivity. The unique synthetic potential of acetylenes is further exploited to access key building blocks for the synthesis of bioactive natural products.Heterocycles are essential structural elements for the bioactivity of natural and synthetic molecules. Among them, tetrahydrofurans and pyrrolidines are particularly important in natural products, such as the antitumoral annonaceous acetogenins gigantecin (1) and squamostatin C (2), 1 or the antibiotic alkaloid preussin (3) (Figure 1). 2 Consequently, the stereoselective synthesis of tetrahydrofurans and pyrrolidines has been extensively investigated. 3 Particularly interesting are methods using cyclization of alcohols or amines onto non-activated olefins combined with a further bond forming event. Iodoetherification or amination reactions have been often used in the synthesis of heterocycles. 4 Recently, the power of metal catalysis has been harnessed to achieve multiple functionalizations of olefins 5 for the synthesis of tetrahydrofurans and pyrrolidines together with further C-N, 6 C-O 7 or C-C bond formation. 8 Impressive progress has been realized in Pd-catalyzed domino reactions involving cyclization on olefins to form a tetrahydrofuran or a pyrrolidine followed by carbonylation, 8a-c vinylation 8d-e or arylation. 8f-j Despite these recent breakthroughs, there are currently no examples of an oxy-or amino-alkynylation reaction for the synthesis of tetrahydrofurans or pyrrolidines. 9 Such a process would be highly useful, as the functionalization of alkynes through cross-coupling, reduction, addition, cyclization, cycloisomerization or cycloaddition gives access to important building blocks used in synthetic chemistry, chemical biology and material sciences. 10 Our group has developed the Pd(II)-catalyzed oxy-and amino-alkynylation of olefins with EBX (ethynyl benziodoxolone) reagent 4 for the synthesis of lactones and lactams (Scheme 1). 11 However, the developed This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organic Letters, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/ol2029383. methods could not be used to access tetrahydrofurans or pyrrolidines and C-C bond formation was limited to primary positions. Herein, we report a different approach for the oxy-and amino-alkynylation of olefins using Pd(0) catalysis and triisopropylsilyl ethynyl bromide (5a), which allowed us to override both limitations (Scheme 1). To the best of our knowledge, this is the first example of Pd(0) catalysis for the oxy-and amino-alkynylation of olefins or for any C-X/C(SP 3 )-C(SP) domino sequence on alkenes. Tetrahydrofurans and pyrrolidines were obtained in good yields an...

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Generation and Trapping of Cyclopentenylidene Gold Species: Four Pathways to Polycyclic Compounds

Cited by 226 publications

References 150 publications

Nature of the Intermediates in Gold(I)‐Catalyzed Cyclizations of 1,5‐Enynes

Nature of the Intermediates in Gold(I)‐Catalyzed Cyclizations of 1,5‐Enynes

Intriguing mechanistic labyrinths in gold(i) catalysis

Pd(0)-Catalyzed Oxy- and Aminoalkynylation of Olefins for the Synthesis of Tetrahydrofurans and Pyrrolidines

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