Enantioselective phosphine-catalyzed [6 + 1] annulations of α-allyl allenoates with 1,1-bisnucleophiles

Lai, Jingxiong; Cai, Wei; Huang, You

doi:10.1039/d4sc02487g

Chem. Sci.

2024

DOI: 10.1039/d4sc02487g

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Enantioselective phosphine-catalyzed [6 + 1] annulations of α-allyl allenoates with 1,1-bisnucleophiles

Jingxiong Lai,

Wei Cai,

You Huang

Abstract: A phosphine catalyzed [6 + 1] annulation of α-allyl allenoates is achieved. Both seven-membered N-heterocycles and carbocycles were synthesized. Mechanistic experiments have verified the 1,6-biselectrophilic intermediate from 1,6-dipole.

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Cited by 4 publications

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Rapid Construction of Cycloheptatriene through Organocatalyzed [4 + 3] Annulation of Coumalates

Zhang,

Han,

Chen

et al. 2024

Org. Lett.

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A protocol for the construction of cycloheptatrienes has been developed. 4-(Dimethylamino)pyridine (DMAP) was found to be an efficient catalyst to promote the [4 + 3] annulation between coumalates and γ-alkyl-substituted allenoate or γ-aryl-3butynoates to deliver a variety of cycloheptatrienes in moderate to good yield with excellent chemoselectivity. The asymmetric version of this annulation was also realized by using bifunctional phosphine catalyst to provide the chiral products with 32−97% ee and 29− 64% yield.

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Rapid Construction of Cycloheptatriene through Organocatalyzed [4 + 3] Annulation of Coumalates

Zhang,

Han,

Chen

et al. 2024

Org. Lett.

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DMAP-Catalyzed [4 + 2] Annulation of Hex-5-en-2-ynoates with Electron-Poor Alkenes

Li,

Wu,

Yang

et al. 2024

Org. Lett.

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Herein, we report a DMAP-catalyzed [4 + 2] annulation reaction of hex-5-en-2-ynoates 1 with electron-poor alkenes 2, which affords exocyclic olefinic cyclohexenes 3 in good yields and excellent regio-, diastereo-, and E/Z selectivities. Distinguished from previous allenoate-or alkynoate-based substrates, hex-5-en-2-ynoates 1 use the βand ε-carbons for the bond formation, presenting new and regiodivergent C 4 synthons for Lewis base-catalyzed annulations.

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Strategic 1,9-Proton-Transfer-Driven Cycloaddition: Synthesis and Stereoselective Contraction of Nine-Membered Heterocycles

Baek,

Lee,

Kang

et al. 2024

ACS Catal.

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We introduce a phosphine-catalyzed cycloaddition involving unprecedented long-range intramolecular proton transfer, facilitating the synthesis of nine-membered heterocycles, which are privileged structures in natural products, as well as potent pharmacophores. Experimental and computational studies revealed that the enamide tether of the N-aromatic zwitterion directly enables long-range regioselective intramolecular proton transfer to proceed independently of outer-sphere proton shuttling. This understanding of selective proton transfer has led to the improved efficiency and regioselectivity of the desired 1,9-proton transfer reaction under anhydrous conditions, thereby advancing the development of higher-order cycloaddition reactions. Further stereoselective contraction of the synthesized nine-membered cyclic compounds using 3-aza-Cope rearrangement demonstrates the synthetic versatility of our approach. The findings of this study not only advance the general understanding of the long-range proton transfer mechanism but also broaden its practical utility in various chemical fields.

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Enantioselective phosphine-catalyzed [6 + 1] annulations of α-allyl allenoates with 1,1-bisnucleophiles

Abstract: A phosphine catalyzed [6 + 1] annulation of α-allyl allenoates is achieved. Both seven-membered N-heterocycles and carbocycles were synthesized. Mechanistic experiments have verified the 1,6-biselectrophilic intermediate from 1,6-dipole.

Cited by 4 publications

References 57 publications

Rapid Construction of Cycloheptatriene through Organocatalyzed [4 + 3] Annulation of Coumalates

Rapid Construction of Cycloheptatriene through Organocatalyzed [4 + 3] Annulation of Coumalates

DMAP-Catalyzed [4 + 2] Annulation of Hex-5-en-2-ynoates with Electron-Poor Alkenes

Strategic 1,9-Proton-Transfer-Driven Cycloaddition: Synthesis and Stereoselective Contraction of Nine-Membered Heterocycles

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