Controlling the Gold(I)-Catalyzed 1,5-Allenene Reaction: Construction of Fused Rings with Excellent Diastereoselectivity

Semleit, Nina; Haberhauer, Gebhard

doi:10.1021/acs.orglett.1c03886

Cited by 8 publications

(16 citation statements)

References 46 publications

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“…Accepted Manuscript yield of 86%. Since the NMR yield for this reaction is good and comparable to our previous results, [32] we omitted to optimize the reaction conditions and immediately extended the scope of application (Scheme 2). For this purpose, the reaction was carried out on a preparative scale in CHCl3 with [JohnPhosAu(NCMe)]SbF6 as catalyst for four hours at room temperature.…”

Section: Accepted Manuscriptsupporting

confidence: 63%

“…It should be noted, that the chlorine atoms in 3 and 7 are not essential for the reaction, however, they increase the yield. [31][32] A gold-catalyzed 1,2addition to alkynes or a dimerization, as reported for other haloalkynes, could not be observed for 3 and 7. [33][34][35] Scheme 2.…”

Section: Accepted Manuscriptmentioning

confidence: 75%

“…This allyl-or benzyl-stabilized carbocation can be captured by nucleophiles. [31][32] In the gold(I)-catalyzed reaction of the 1,5-allenenes 4 with acetylenes 5, the polycycles 6 are obtained, with four new C-C bonds being formed in only a single reaction step (Scheme 1b). [31] The gold(I)-catalyzed cyclization of the 1,5-allenene 8 in the presence of various carbon and oxygen nucleophiles led to the formation of the 6−6−5 This article is protected by copyright.…”

Section: Accepted Manuscriptmentioning

confidence: 99%

“…From our previous work, we were aware that [JohnPhosAu(NCMe)]SbF6 [36] is the most suitable catalyst for the gold(I)-catalyzed activation of aryl propargyl ethers. [31][32] According to NMR experiments the bicycles 10 are formed via the 1,5-allenene 4. Using 1,3,5trimethoxybenzene as nucleophile in an NMR experiment, product 10h was observed with a This article is protected by copyright.…”

Section: Accepted Manuscriptmentioning

confidence: 99%

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Gold(I)-Catalyzed Dearomatization–Allenene Reaction for the Construction of Polycycles with Excellent Diastereoselectivity

Semleit

Haberhauer

2023

Synthesis

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The synthesis of complex polycycles starting from simple building blocks in just a few reaction steps is usually very challenging. Herein, we present the gold(I)-catalyzed synthesis of various polycycles via dearomatization–allenene reaction of aryl propargyl ethers with different nucleophiles. Depending on the starting material, polycycles can be isolated in yields up to 94% and with an enantiomeric excess of 95%. Quantum chemical calculations show that for all starting materials a Claisen rearrangement to the allenene occurs in the first reaction sequence. The subsequent cyclization and reaction with a nucleophile leads to various polycycles with the formation of up to six new C–C bonds in only one reaction step. All reactions proceed with excellent diastereoselectivity, with a α-quaternary carbonyl carbon present in the products.

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Section: Accepted Manuscriptsupporting

confidence: 63%

Section: Accepted Manuscriptmentioning

confidence: 75%

Section: Accepted Manuscriptmentioning

confidence: 99%

Section: Accepted Manuscriptmentioning

confidence: 99%

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Gold(I)-Catalyzed Dearomatization–Allenene Reaction for the Construction of Polycycles with Excellent Diastereoselectivity

Semleit

Haberhauer

2023

Synthesis

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“…We started our investigations using [JohnPhosAu(NCMe)]SbF 6 as catalyst, as we have previously obtained very good results employing this catalytic system for the reaction of haloalkynes. [35][36][37][46][47][48][49] The first reaction in toluene at 80 °C led to the selective formation of a product with an NMR yield of 59 % (Table 1, entry 1). The reaction was repeated on a preparative scale and a single product could be isolated.…”

Section: Experimental Studiesmentioning

confidence: 99%

Regio‐ and Stereoselective Synthesis of Ynenamides through Gold(I)‐Catalyzed Hydroalkynylation of Ynamides

et al. 2022

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Transition metal catalysis is a useful tool for C−C bond‐forming reactions. Of special interest is the hydroalkynylation reaction of alkynes, which provides a simple method for the synthesis of enynes representing interesting structural motifs in organic chemistry. So far, there are only a few examples of gold(I)‐catalyzed hydroalkynylation reactions. Herein, we were able to show experimentally that the gold(I)‐catalyzed hydroalkynylation of ynamides leads regio‐ and stereoselectively to the corresponding ynenamides, a rather unknown type of molecule. A wide range of products could be generated with yields up to 90 % and, in contrast to many other gold‐catalyzed alkyne dimerization reactions, alkyl groups are tolerated. Quantum chemical calculations and NMR labelling experiments reveal a mechanism via dual gold catalysis.

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Highlighting the Rich Chemistry of the Allenone Moiety

Almendros

Alonso

2023

Adv Synth Catal

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Conjugated and non-conjugated allenones appear as recurring motifs in organic synthesis, natural products and mechanistic investigations showing unique properties and applications. The ability of allenones to build cycles has provided a direct access to strained systems, medium-sized rings, arenes, heterocycles and complex polycycles. In addition, allenones have served as models in mechanistic investigations and catalysis. The critic compilation herein presented will provide an exhaustive overview of the synthetic possibilities allenones may offer, which certainly will inspire our community in their search of more efficient synthetic methodologies, preparation of biological and pharmaceutical targets, and improve our knowledge in theoretical organic chemistry. Great part of this review will discuss synthetic aspects, catalysis innovation and mechanistic insights of the chemical transformations implying the allenone motif. In addition, many examples on total synthesis and pharmacologically active compounds will be described. We hope that this overview will be attractive to the organic chemistry, synthetic chemistry, catalysis, theoretical chemistry, natural products and medicinal chemistry communities. 3.5. Synthesis of Spirocycles and Bridged Structures 3.6. Open-Chain Structures from Allenones 3.7. Allenones in Total Synthesis 4.

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Controlling the Gold(I)-Catalyzed 1,5-Allenene Reaction: Construction of Fused Rings with Excellent Diastereoselectivity

Cited by 8 publications

References 46 publications

Gold(I)-Catalyzed Dearomatization–Allenene Reaction for the Construction of Polycycles with Excellent Diastereoselectivity

Gold(I)-Catalyzed Dearomatization–Allenene Reaction for the Construction of Polycycles with Excellent Diastereoselectivity

Regio‐ and Stereoselective Synthesis of Ynenamides through Gold(I)‐Catalyzed Hydroalkynylation of Ynamides

Highlighting the Rich Chemistry of the Allenone Moiety

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