Diene Synthesis by the Reductive Transposition of 1,2-Allenols

Rinaolo, Vincent J.; Robinson, Emily E.; Diagne, Abdallah B.; Schaus, Scott E.; Thomson, Regan J.

doi:10.1055/s-0039-1690692

Cited by 5 publications

(4 citation statements)

References 11 publications

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Section: Synthetic Utilitymentioning

confidence: 99%

“…Opposite to previously mentioned [3,3]-sigmatropic rearrangements, the reaction course proceeded with a notable lack of stereoselectivity, yielding cis/trans dienes in rates from 3:1 to 1:1 (Scheme 32, reaction c). 191 Preprepared HCl or HBr solutions in ether or ethyl acetate are reported to promote the isomerization of (1-hydroxybuta-2,3dien-2-yl)diphenylphosphine oxides 179 into chlorinated or brominated phosphinoyl 1,3-butadienes 180. The methodology is applied to primary alcohols, and no stereocontrol is stated at the C3−C4 double bond.…”

Section: Enantioenriched Allenolsmentioning

confidence: 99%

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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: Synthetic Utilitymentioning

confidence: 99%

Section: Enantioenriched Allenolsmentioning

confidence: 99%

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

2021

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“…More recently, Rinaolo et al developed a methodology for the synthesis of 1,3-dienes via reductive transposition of allenols ( Scheme 63 ) [ 202 ]. Reaction of 1,2-allenols with N -isopropylidene- N ′-2-nitrobenzenesulfonyl hydrazine (IPNBSH) under Mitsunobu conditions [PPh 3 /diethyl azodicarboxylate(DEAD)] generated in situ the corresponding monoalkyl diazene intermediate, which upon treatment with trifluoroethanol provided through the loss of dinitrogen, 1,3-dienes in good yields albeit in moderate Z -selectivity.…”

Section: Rearrangement/isomerizationmentioning

confidence: 99%

Modern Synthetic Methods for the Stereoselective Construction of 1,3-Dienes

Soengas

Rodríguez‐Solla

2021

Molecules

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The 1,3-butadiene motif is widely found in many natural products and drug candidates with relevant biological activities. Moreover, dienes are important targets for synthetic chemists, due to their ability to give access to a wide range of functional group transformations, including a broad range of C-C bond-forming processes. Therefore, the stereoselective preparation of dienes have attracted much attention over the past decades, and the search for new synthetic protocols continues unabated. The aim of this review is to give an overview of the diverse methodologies that have emerged in the last decade, with a focus on the synthetic processes that meet the requirements of efficiency and sustainability of modern organic chemistry.

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“…Approaches based on C–H activation, photoredox catalysis, and metathesis have also been described . Notably, the stereoselective preparation of substituted dienes has been achieved by rearrangements, transpositions, or isomerizations of allenes and alkynes, albeit with a narrow substrate scope . Examples of conjugated dienes obtained by alkene isomerization are scarce (Figure B) .…”

mentioning

confidence: 99%

Kinetically Controlled Stereoselective Access to Branched 1,3-Dienes by Ru-Catalyzed Remote Conjugative Isomerization

Scaringi

Mazet

2021

ACS Catal.

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A Ru-catalyzed conjugative isomerization of remote alkenes that affords branched 1,3-dienes is described. These kinetic products are obtained in high yields, good levels of regiocontrol, and high stereoselectivity. A broad range of functional groups and heterocycles are compatible with the mild reaction conditions, and isomerization is sustained over long distances. Control experiments support a metal-hydride mechanism consisting of iterative migratory insertions/β-H eliminations, which is initiated preferentially at the terminal olefinic site. Two one-pot multimetallic selective catalytic sequences using [Ru/Cu] and [Ru/Rh] combinations have been developed to illustrate the synthetic potential of the process.

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Diene Synthesis by the Reductive Transposition of 1,2-Allenols

Abstract: Monoalkyl diazene species are versatile intermediates that have enabled many useful synthetic transformations in complex chemical environments. Herein we report the reductive transposition of 1,2-allenols for the direct synthesis of dienes through an alkene walk process.

Cited by 5 publications

References 11 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

Modern Synthetic Methods for the Stereoselective Construction of 1,3-Dienes

Kinetically Controlled Stereoselective Access to Branched 1,3-Dienes by Ru-Catalyzed Remote Conjugative Isomerization

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