Stereospecific synthesis of allylic and homoallylic alcohols from functionalized propargylic alcohols

Sydnes, Leiv K.; Holmelid, Bjarte; Kvernenes, Ole H.; Valdersnes, Stig; Hodne, Mari; Boman, Kjartan

doi:10.3998/ark.5550190.0009.e23

Cited by 14 publications

(7 citation statements)

References 9 publications

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“… a Stepwise yields are for compounds 2 , 3 , and 4 obtained in steps 1−3 (S1 − S3), respectively. b Isolated yield after reductive workup as described in ref …”

Section: Resultsmentioning

confidence: 99%

“…4,4,5,5-Tetraethoxypent-2-yn-1-ol ( 2a ), 5,5,6,6-tetraethoxyhex-3-yn-2-ol ( 2b ), 6,6,7,7-tetraethoxy-2,2-dimethylhept-4-yn-3-ol ( 2d ), 4,4,5,5-tetraethoxy-1-phenylpent-2-yn-1-ol ( 2e ), and 1,1,2,2-tetraethoxyundec-3-yn-5-ol ( 2f ) were synthesized as described in the literature whereas 6,6,7,7-tetraethoxy-2-methylhept-4-yn-3-ol ( 2c ) was prepared as follows.…”

Section: Methodsmentioning

confidence: 99%

“…We have reported a simple and efficient synthesis of 3,3,4,4-tetraethoxybutyne (TEB) ( 1 ), using ethyl vinyl ether as starting material and taking advantage of the serendipitous discovery that 1,1,2-trihalocyclopropanes undergo ring-opening under phase-transfer conditions in the presence of ethanol . Easy access to TEB has made the preparation of 1-substituted 4,4,5,5-tetraethoxypent-2-yn-1-ols ( 2 ) straightforward (Scheme ). − These alcohols are highly functionalized, and by selectively exploiting their reactive moieties, syntheses of a range of interesting compounds can be envisaged and are being investigated.…”

Section: Introductionmentioning

confidence: 99%

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New Regiospecific Synthesis of Tri- and Tetra-Substituted Furans

et al. 2009

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Beta-acyloxy alpha,beta-unsaturated acetylenic ketones have been shown to react with organocuprate reagents and undergo cyclization followed by dehydration to give substituted furans as the final products. The transformation appeared to be versatile, and tri- and tetra-substituted furans were obtained with regiochemical control in moderate to good yields. The best yields were generally obtained when the reactions were performed around -60 degrees C with substrates and cuprates containing sterically demanding substituents. The proposed mechanism for furan formation has been supported by experiments.

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“… a Stepwise yields are for compounds 2 , 3 , and 4 obtained in steps 1−3 (S1 − S3), respectively. b Isolated yield after reductive workup as described in ref …”

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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New Regiospecific Synthesis of Tri- and Tetra-Substituted Furans

et al. 2009

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“…521 Sydnes and co-workers reported on the semihydrogenation of a functionalized ynone (703) by means of the Lindlar's catalyst, which gave the corresponding cis-product (704) in excellent yield and diastereoselectivity (Scheme 312). 522 To conclude, few reports have been published on the semihydrogenation of functionalized ynones: with PPh 3 /H 2 O, (E)-enones were obtained, whereas the Lindlar's catalyst gave the expected (Z)-diastereomers.…”

Section: Reduction Of the Triple Bondmentioning

confidence: 99%

Conjugated Ynones in Organic Synthesis

2019

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This review article will consider the preparation and application of ynones in synthetic organic chemistry. Concerning the preparation of these bifunctional compounds, several methodologies starting from propargyl alcohols, acyl derivatives, both by using alkynylmetal reagents or by transition metal (mainly palladium and copper) catalyzed alkynylations, carbon monoxide (carbonylation of terminal alkynes and alkenes), and other substrates will be discussed. The reactivity and synthetic applications of ynones will be focused on conjugate additions with boron-, carbon-, nitrogen-, oxygen-, and other heteroatom-containing nucleophiles, as well as radicals. Then, cycloaddition processes will include [2 + 2] cycloadditions, [3 + 2] 1,3-dipolar cycloadditions (with azides, nitrones, azomethine imines and ylides, nitrile oxides, diazo compounds, and other dipoles), and [4 + 2] cycloadditions (mainly Diels–Alder-type reactions). The reduction of the triple bond, addition to the carbonyl group (using carbon- and heteronucleophiles and reductions), and other not so commonly used processes (such as aldol reactions, cyclizations, and isomerizations) will be considered at the end.

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“…TEB possesses a significant potential as a synthon in organic synthesis. The reagent has been utilized to prepare a variety of compounds such as unsaturated alcohols, deoxygenated carbohydrates, furans, and a number of other heterocyclic compounds…”

Section: Introductionmentioning

confidence: 99%

Multivariate Optimization of a Cyclopropanation, the Key Step in the Synthesis of 3,3,4,4-Tetraethoxybut-1-yne

Shang

Terranova

Sydnes

et al. 2014

Org. Process Res. Dev.

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Tetraethoxybut-1-yne (TEB) is a versatile synthon that can be produced in a four-step synthesis. The third step of the synthesis is a cycloproanation, which has been thoroughly investigated and optimized by means of statistical experimental design and multivariate modeling. At the outset, an exhaustively pre-experimental design was performed resulting in a copious Ishikawa cause−effect diagram. In total six of the experimental variables were assessed to be of large importance and thus selected for further investigation by fractional factorial design. The results of that screening and first step optimization formed the basis for a response surface modeling (RSM) study. The RSM investigation was completed by using a central composite design from which a response surface was graphically produced as an iso-contour projection. The derived multivariate predictive model in terms the iso-contour projection plots were ultimately utilized to establish experimental conditions that concomitantly provided excellent yield (>99%) and minimized amounts of inputs and thus obtain the desired product at the lowest production cost and minimized side-streams.

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Stereospecific synthesis of allylic and homoallylic alcohols from functionalized propargylic alcohols

Cited by 14 publications

References 9 publications

New Regiospecific Synthesis of Tri- and Tetra-Substituted Furans

New Regiospecific Synthesis of Tri- and Tetra-Substituted Furans

Conjugated Ynones in Organic Synthesis

Multivariate Optimization of a Cyclopropanation, the Key Step in the Synthesis of 3,3,4,4-Tetraethoxybut-1-yne

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