Gold‐Catalyzed Double Cycloisomerization of 1‐Ene‐4,10‐diynyl Esters to Bicyclo[6.3.0]undeca‐2,4,9‐trienyl Esters

Mathiew, Mitch; Tan, Javey Khiapeng; Chan, Philip Wai Hong

doi:10.1002/ange.201809376

Angewandte Chemie

2018

DOI: 10.1002/ange.201809376

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Gold‐Catalyzed Double Cycloisomerization of 1‐Ene‐4,10‐diynyl Esters to Bicyclo[6.3.0]undeca‐2,4,9‐trienyl Esters

Mitch Mathiew

Javey Khiapeng Tan

Philip Wai Hong Chan

Abstract: A synthetic method to prepare bicyclo[6.3.0]undeca‐2,4,9,trienyl esters efficiently from gold(I)‐catalyzed Rautenstrauch rearrangement/1,5‐hydride shift/8‐endo‐dig cyclization of 1‐ene‐4,10‐diynyl esters is described. The suggested double cycloisomerization mechanism delineates the first example of an unactivated all‐carbon tethered 1,7‐enyne, either preformed or formed in situ, which undergoes an 8‐endo‐dig cyclization pathway to give a cyclooctane motif. It also offers an extremely rare synthetic method in o… Show more

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Cited by 7 publications

References 70 publications

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Gold‐ and Brønsted Acid‐Catalysed Deacyloxylative Cycloaromatisation of 1,6‐Diyne Esters to 11H‐Benzo[a]fluorenes and 13H‐Indeno[1,2‐l]phenanthrenes

Chan

Baratay

et al. 2022

Adv Synth Catal

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A synthetic method to prepare 11Hbenzo [a]fluorenes and 13H-indeno[1,2l]phenanthrenes that relies on the gold(I)-and Brønsted acid-mediated deacyloxylative cycloaromatisation of 1,6-diyne esters under reaction conditions that did not require the exclusion of moisture or air is described. The reaction mechanism was delineated to involve an initial gold(I)-catalysed 1,2-acyloxy migration and 5-exo-trig cyclisation pathway. This was followed by 1,5-enyne rearrangement and Brønsted acid-assisted deacyloxylative aromatisation to give the polyaromatic hydrocarbon (PAH) product.

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Gold‐ and Brønsted Acid‐Catalysed Deacyloxylative Cycloaromatisation of 1,6‐Diyne Esters to 11H‐Benzo[a]fluorenes and 13H‐Indeno[1,2‐l]phenanthrenes

Chan

Baratay

et al. 2022

Adv Synth Catal

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Stereoselective Access to Polyfunctionalized Nine‐Membered Heterocycles by Sequential Gold and Palladium Catalysis

Yang

Zhao

2021

Angewandte Chemie

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We report herein a gold and palladium sequential catalysis system to access furan-fused nine-membered heterocycles in high efficiency and enantioselectivity. In this one-pot procedure, easily accessible enynamides undergo cyclization to generate azadienes in situ that participate in enantioselective formal [5+4] cycloaddition with vinyl ethylene carbonates. Conformation-controlled highly diastereoselective derivatizations of these medium-sized rings, coupled with oxidative furan cleavage, have enabled the access to diverse densely-functionalized nine-membered lactams.Medium-sized heterocycles (8 to 11-membered rings) are important structural motifs in various bioactive natural products. [1] The synthesis of these medium-sized rings, however, still remains a great challenge for catalytic method development. Out of the different synthetic strategies developed for medium-sized ring formation, intramolecular cyclization or ring expansion is most explored. [2,3] As an alternative and synthetically flexible approach, intermolecular dipolar cycloaddition provides a significant advantage of directly coupling two building blocks (serving as dipoles and dipolarophiles) to produce medium-sized heterocycles. [4] However, success along these lines remains limited, with cycloaddition of only a few classes of 1,4-dipolarophiles reported in the literature. Our group has introduced a dihydrobenzofuran-derived azadiene [5] to realize highly stereoselective Pd-catalyzed cycloadditions for the preparation of nine-or ten-membered benzofuran/indole-fused heterocycles. [5b-d] The same substrate was also used by the Lu group to achieve phosphine-catalyzed enantioselective eight-membered heterocycle synthesis. [6] The Shibata group has introduced CF 3 -substituted benzooxazinones for Pd-catalyzed decarboxylative cycloaddition to access benzo-fused nine-or twelve-membered heterocycles. [7] The formal [5+4] cycloaddition using ortho-quinone methides to access enantioenriched benzo-fused nine-membered rings have also been reported by the Fan group and the Guo group. [8] Despite these advances, it is important to note that due to the special Scheme 1. Diverse nine-membered heterocycles prepared from in situ generated azadienes.

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Eisen‐katalysierte Cycloisomerisierung und C−C‐Bindungsaktivierung als Zugang zu nicht‐kanonischen tricyclischen Cyclobutanen

et al. 2022

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Cycloisomerisierungen sind leistungsfähige Gerüstumlagerungen, die den atomökonomischen Aufbau komplexer molekularer Architekturen erlauben. Wir präsentieren hier eine ungewöhnliche Art der Cyclopropyl-Enin-Cycloisomerisierung, die den Prozess der Cycloisomerisierung mit der Aktivierung einer CÀ C Bindung in Cyclopropanen verbindet. Es wurde eine Vielzahl substituierter nicht-kanonischer tricyclischer Cyclobutane unter milden Bedingungen mit [(Ph 3 P) 2 Fe-(CO)(NO)]BF 4 als Katalysator in guten bis exzellenten Ausbeuten und hoher Stereokontrolle synthetisiert. Cycloisomerisierungen ermöglichen den Aufbau komplexerannelierter Ringsysteme ausgehend von leicht zugänglichen Ausgangsmaterialien. Die Bedeutung dieses Forschungsgebiets spiegelt sich in der Anzahl der Veröffentlichungen wider. [1] Während Rh- [2] und Ir-Komplexe [3] diesen Bereich der Chemie klar dominierten, eröffnete die Einführung definierter Au I -Komplexe als π-Lewis-Säure-Katalysatoren neue mechanistische Wege. [4] Kürzlich berichteten wir, dass der kationische 16-Elektronen-Fe 0 -Komplex [(Ph 3 P) 2 Fe-(CO)(NO)]BF 4 2 in redoxneutralen Cycloisomerisierungen von Eninacetaten oder Aryl-Allenyl-Ketonen als π-Lewis-Säure-Katalysator agiert [Gl. (1), Schema 1]. [5] Zu Cycloisomerisierungen von cyclopropyl-substituierten Eninen 5 leisteten Wender [6a-c] sowie Shintani/Hayashi [6d] wegweisende Pionierarbeit, wobei diese Rh-Komplexe zur Darstellung der Produkte durch eine formale [5+2]-Cycloaddition verwendeten [Gl. ( 2), Schema 1]. Echavarren nutzte die Eigenschaft von Au I -Komplexen, als π-Lewis-Säuren reagieren zu können, in einer bemerkenswerten Studie zu Cycloisomerisierungen von Cyclopropyl-substituierten Eninen wie z. B. Molekül 7 [Gl. (3), Scheme 1]. [7] Im Gegensatz zur Rh-Katalyse lieferte die Cyclosiomerisierung nicht das Produkt der [5+2]-Cycloaddition sondern den 5,5,4-Tricyclus 8 durch eine Cycloisomerisierung-Prins-Cyclisierung [Gl. (3), Schema 1].

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Gold‐Catalyzed Double Cycloisomerization of 1‐Ene‐4,10‐diynyl Esters to Bicyclo[6.3.0]undeca‐2,4,9‐trienyl Esters

Cited by 7 publications

References 70 publications

Gold‐ and Brønsted Acid‐Catalysed Deacyloxylative Cycloaromatisation of 1,6‐Diyne Esters to 11H‐Benzo[a]fluorenes and 13H‐Indeno[1,2‐l]phenanthrenes

Gold‐ and Brønsted Acid‐Catalysed Deacyloxylative Cycloaromatisation of 1,6‐Diyne Esters to 11H‐Benzo[a]fluorenes and 13H‐Indeno[1,2‐l]phenanthrenes

Stereoselective Access to Polyfunctionalized Nine‐Membered Heterocycles by Sequential Gold and Palladium Catalysis

Eisen‐katalysierte Cycloisomerisierung und C−C‐Bindungsaktivierung als Zugang zu nicht‐kanonischen tricyclischen Cyclobutanen

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