Palladium(II)‐Catalyzed Oxidative Carbocyclization of Aza‐Enallenes

Persson, Andreas K. Å.; Bäckvall, Jan‐E.

doi:10.1002/anie.201000726

Cited by 115 publications

(21 citation statements)

References 44 publications

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“…Bäckvall 102 recently published a novel Pd(II)-catalyzed oxidative carbocyclization methodology (Scheme 98). Under these conditions, allenamides 367 could cyclize to afford the corresponding dihydropyrrole derivatives 368 .…”

Section: Reactions Of Allenamidesmentioning

confidence: 99%

Allenamides: A Powerful and Versatile Building Block in Organic Synthesis

et al. 2013

Chem. Rev.

332

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Section: Reactions Of Allenamidesmentioning

confidence: 99%

Allenamides: A Powerful and Versatile Building Block in Organic Synthesis

et al. 2013

Chem. Rev.

332

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“…[1,2] Processes involving the allene moiety together with another hydrocarbon unsaturation have attractedc onsiderable attention recently. [5][6][7] In these reactions a coordinated allene attacks palladium via aC ÀHb ond cleavage to generate the key reactive vinylpalladium intermediate. [5][6][7] In these reactions a coordinated allene attacks palladium via aC ÀHb ond cleavage to generate the key reactive vinylpalladium intermediate.…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Insight into Enantioselective Palladium‐Catalyzed Oxidative Carbocyclization–Borylation of Enallenes

Qiu

Mendoza

Posevins

et al. 2018

Chemistry A European J

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The asymmetric palladium-catalyzed oxidative carbocyclization-borylation of enallenes, employing a chiral phosphoric acid as co-catalyst, constitutes an efficient and convenient entry into functionalized building blocks with cyclopentene scaffolds in high enantiopurity. Up till now there has been a lack of knowledge concerning the origin of enantioselectivity of this reaction as well as the absolute configuration of the product. Herein, we report the crystal structure of one of the compounds generated via this carbocyclization, providing the link between the configuration of the products and the configuration of the chiral phosphoric acid used in the reaction. Furthermore, the origin of the enantioselectivity is thoroughly investigated with density functional theory (DFT) calculations. By careful examination of different possible coordination modes, it is shown that the chiral phosphoric acid and the corresponding phosphate anion serve as ligands for palladium during the key stereoselectivity-determining cyclization step. In addition, we examine reactions wherein an extra chiral reagent, a p-benzoquinone containing a chiral sulfoxide, is used. The combined experimental and theoretical studies provide insight into the details of complexation of palladium with various species present in the reaction mixture, furnishing a general understanding of the factors governing the stereoselectivity of this and related catalytic reactions.

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“…Late transition metal complexes of Ru, Rh, Ir, Pd, Pt, and Cu are effective catalysts for the hydroamination reaction. 104,105 In 2012, Messerle and coworkers 87 reported a series of cationic rhodium (133,135) and iridium complexes (134,136) with bidentate N,N 0 -pyrazolyl-triazolyl ligands (Fig. 3).…”

Section: Synthesis Of 1-pyrrolines By Iron Catalysis In 2012mentioning

confidence: 99%

“…Bäckvall reported the carbocyclization of aza-enallenes 254 in the presence of catalytic Pd(OAc) 2 to give the 2-pyrrolines 255 (Scheme 82). 135 Several substitution patterns on both the alkene 252 and allene 253 were well tolerated, providing moderate to high yields of the nal pyrrolines (64-95%) (Scheme 82).…”

Section: Synthesis Of 2-pyrrolines By Palladium Catalysismentioning

confidence: 99%