Asymmetric [2,3]-Wittig Rearrangement: Synthesis of Homoallylic, Allenylic, and Enynyl α-Benzyl Alcohols

Rodríguez, Ricardo I.; Ramírez, Elsie; Fernández‐Salas, José A.; Sánchez‐Obregón, Rubén; Yuste, Francisco; Alemán, José V.

doi:10.1021/acs.orglett.8b03659

Cited by 13 publications

(4 citation statements)

References 56 publications

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“…More recently, a Wittig-based methodology was also employed for the synthesis of a family of substituted asymmetric α-allenols 68 . In this case, a remote chiral sulfoxide in the starting propargylic ether 67 was responsible of the stereochemistry, behaving as a chiral inductor rather than a chirality transfer agent (Scheme , reaction b) . In both cases, good diastereoselectivities were achieved, although no axial chirality is described, and the lack of a wider scope in the methodology leaves much work yet to be explored in this field.…”

Section: Synthesis Of Allenolsmentioning

confidence: 99%

Deciphering the Chameleonic Chemistry of Allenols: Breaking the Taboo of a Onetime Esoteric Functionality

2021

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The allene functionality has participated in one of the most exciting voyages in organic chemistry, from chemical curiosities to a recurring building block in modern organic chemistry. In the last decades, a special kind of allene, namely, allenol, has emerged. Allenols, formed by an allene moiety and a hydroxyl functional group with diverse connectivity, have become common building blocks for the synthesis of a wide range of structures and frequent motif in naturally occurring systems. The synergistic effect of the allene and hydroxyl functional groups enables allenols to be considered as a unique and sole functionality exhibiting a special reactivity. This Review summarizes the most significant contributions to the chemistry of allenols that appeared during the past decade, with emphasis on their synthesis, reactivity, and occurrence in natural products.

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Section: Synthesis Of Allenolsmentioning

confidence: 99%

Deciphering the Chameleonic Chemistry of Allenols: Breaking the Taboo of a Onetime Esoteric Functionality

2021

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“…Among the several approaches that have been employed for their synthesis [37][38][39][40][41][42][43][44][45], the [2,3]-Wittig rearrangement of propargylic ethers represents an efficient way to assemble them [46,47]. The major limitation of this versatile bond reorganization process, which has many other applications in organic synthesis, is mainly correlated to the use of strong bases and very low temperatures together with the laborious, complicated, and expensive procedures required [48][49][50].…”

Section: Introductionmentioning

confidence: 99%

Experimental and Theoretical DFT Investigations in the [2,3]-Wittig-Type Rearrangement of Propargyl/Allyl-Oxy-Pyrazolones

et al. 2021

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Here we report the synthesis of interesting 3-alkyl-4-hydroxy-1-aryl-4-(propa-1,2-dienyl)1H-pyrazol-5(4H)-ones and 9-alkyl-7-aryl-1-oxa-7,8-diazaspiro[4.4]nona-3,8-dien-6-ones, starting from 1,2-diaza-1,3-dienes (DDs) and propargyl alcohol. The reaction proceeds through a sequence Michael-type nucleophilic attack/cyclization/[2,3]-Wittig rearrangement. In the same way, the reaction between the aforementioned DDs and allyl alcohol furnished 4-allyl-4-hydroxy-3-alkyl-1-aryl-1H-pyrazol-5(4H)-ones. A DFT study was also carried out, in order to have decisive clarifications about the mechanism.

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“…The construction of α-hydroxyallenes has attracted considerable attention for decades, and several catalytic enantioselective synthetic methods have been developed, such as desymmetrization reaction, Aldol-like reaction, arylboration reaction, Petasis reaction, and rearrangement reaction . Among them, [2,3]-Wittig rearrangement , of propargylic ethers provides an efficient and facile route to elaborated functionalized α-hydroxyallenes. Recently, our group described an asymmetric propargyl [2,3]-Wittig rearrangement of oxindole derivatives using a chiral N , N ′-dioxide/Ni II complex, and the corresponding 3-hydroxy 3-substituted oxindoles bearing an allenyl group were obtained in good results (Scheme a) .…”

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confidence: 99%

Kinetic Resolution of Propargylic Ethers via [2,3]-Wittig Rearrangement to Synthesize Chiral α-Hydroxyallenes

Dong

Feng

et al. 2020

Org. Lett.

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An efficient kinetic resolution of propargyloxy dicarbonyl compounds via asymmetric [2,3]-Wittig rearrangement was achieved by using a chiral N,N′-dioxide/NiII complex catalyst. Various chiral α-allenyl alcohols were obtained in high enantioselectivities under mild conditions. The utility of this method was readily demonstrated in the asymmetric synthesis of the chiral 2,5-dihydrofuran derivative.

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Asymmetric [2,3]-Wittig Rearrangement: Synthesis of Homoallylic, Allenylic, and Enynyl α-Benzyl Alcohols

Abstract: H and 13 C spectra for all new compounds and X-ray data for 2e′ and 7a (PDF)Accession Codes CCDC 1875997 and 1875998 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk

Cited by 13 publications

References 56 publications

Deciphering the Chameleonic Chemistry of Allenols: Breaking the Taboo of a Onetime Esoteric Functionality

Deciphering the Chameleonic Chemistry of Allenols: Breaking the Taboo of a Onetime Esoteric Functionality

Experimental and Theoretical DFT Investigations in the [2,3]-Wittig-Type Rearrangement of Propargyl/Allyl-Oxy-Pyrazolones

Kinetic Resolution of Propargylic Ethers via [2,3]-Wittig Rearrangement to Synthesize Chiral α-Hydroxyallenes

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