Conjugate addition of vinylic organocuprates generated via transmetalation of phenylseleno‐substituted vinylzirconates: Functionalization at the 4‐position of enones

Segi, Masahito; Suzuki, Masahiro; Shintaku, Kazuki; Maeda, Hideaki

doi:10.1002/hc.20720

Cited by 6 publications

(9 citation statements)

References 13 publications

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“…1 H, 13 and distilled under reduced pressure. Other reagents were commercially available and used without further purification.…”

Section: Methodsmentioning

confidence: 99%

“…All reactions were performed under an argon atmosphere with flame-dried glassware using a vacuum pump unless otherwise described. 4-(Phenylselanyl)but-1-yne (1) 13 and trimethyl(tributylstannyl)silane 15 were synthesized according to published procedures. 1, 11.2, 13.7, 27.4, 27.5, 29.2, 47.2, 126.8, 129.0, 130.4, 133.0, 145.4, 163.…”

Section: Methodsmentioning

confidence: 99%

“…1 H NMR (400 MHz, CDCl 3 ): δ = -0.17 (s, 9 H), 3.83 (s, 3 H), 4.77 (d, J = 17.3 Hz, 1 H), 5.10 (d, J = 10.7 Hz, 1 H), 5.82 (s, 1 H), 6.60 (dd, J = 10.7, 17.3 Hz, 1 H), 6.87 (d, J = 8.8 Hz, 2 H), 7.05 (d, J = 8.8 Hz, 2 H). 13 C NMR (100 MHz, CDCl 3 ): δ = -0. 18, 55.2, 113.1, 116.7, 130.5, 132.5, 134.2, 143.2, 156.0, 158.7.…”

Section: Lrms (Eimentioning

confidence: 99%

“…1 H NMR (400 MHz, CDCl 3 ): δ = -0.18 (s, 9 H), 4.61 (d, J = 17.4 Hz, 1 H), 5.15 (d, J = 10.5 Hz, 1 H), 5.95 (s, 1 H), 6.60 (dd, J = 10.5, 17.4 Hz, 1 H), 7.32 (d, J = 8.1 Hz, 2 H), 8.22 (d, J = 8.1 Hz, 2 H). 13 C NMR (100 MHz, CDCl 3 ): δ = -0. 28, 117.4, 123.1, 130.4, 135.9, 142.2, 147.1, 147.5, 153.8 -0.21, 117.0, 128.0, 130.8, 133.0, 135.0, 138.6, 142.8, 155.0.…”

Section: Lrms (Eimentioning

confidence: 99%

“…10e Recently, we reported the stereoselective synthesis of monosubstituted 1,3-dienes via conjugated addition of vi-nylic organocuprates, generated from the transmetalation of vinylzirconates, containing a phenylselanyl group to enones, followed by selenoxide elimination via oxidation. 13 Herein, we describe a simple and stereoselective synthesis of (Z)-1-silyl-2-aryl-1,3-dienes by the combination of palladium-catalyzed silylstannylation of the terminal triple bond of 4-(phenylselanyl)but-1-yne (1), oxidative elimination of the phenylselanyl group, and the Stille coupling reaction with various aryl iodides (Scheme 1).…”

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confidence: 99%

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A Stereoselective Approach to (Z)-1-Silyl-2-aryl-1,3-dienes from 4-(Phenylselanyl)but-1-yne via Palladium-Catalyzed Silylstannylation and Selenoxide Elimination

2013

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The palladium-catalyzed silylstannylation of 4-(phenylselanyl)but-1-yne proceeded regio-and stereoselectively, followed by selenoxide elimination via oxidation to give (Z)-1-(trimethylsilyl)-2-(tributylstannyl)buta-1,3-diene in good yield. This conjugated diene underwent the Stille coupling reaction with various aryl iodides in the presence of Pd(PPh 3 ) 4 to afford (Z)-2-aryl-1-(trimethylsilyl)buta-1,3-dienes with high stereoselectivity. Reversing the order of selenoxide elimination and Stille coupling reaction in the synthetic procedure also resulted in good yields of (Z)-2-aryl-1-(trimethylsilyl)buta-1,3-dienes.

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“…1 H, 13 and distilled under reduced pressure. Other reagents were commercially available and used without further purification.…”

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Lrms (Eimentioning

confidence: 99%

Section: Lrms (Eimentioning

confidence: 99%

mentioning

confidence: 99%

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A Stereoselective Approach to (Z)-1-Silyl-2-aryl-1,3-dienes from 4-(Phenylselanyl)but-1-yne via Palladium-Catalyzed Silylstannylation and Selenoxide Elimination

2013

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Hydrozirconation of Alkynes

Milligan,

Hammill,

Crocker

et al. 2023

Organic Reactions

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Since the first preparation of organozirconocenes from alkenes and alkynes in 1972, hydrozirconation has become one of the most commonly used stoichiometric methods to convert readily available starting materials into reactive but stable organometallic intermediates. A broad range of subsequent transformations may be employed to convert organozirconocenes in situ into high‐value functionalized products, often with the strategic formation of one (or several) new carbon–carbon bonds. This chapter focuses on the hydrozirconation of terminal and internal alkynes, and the subsequent synthetic transformations of the resulting alkenylzirconocenes. Zirconocene hydrochloride, Cp 2 Zr(H)Cl, is most frequently employed for the hydrozirconation step and can be used as a reagent or prepared in situ. Subsequent reactions of alkenylzirconocenes include additions to inorganic electrophiles such as halogens, as well as in situ ligand transfers to other metals, such as palladium and zinc, that further expand the range of accessible bond formations. The initial discussion focuses on the mechanism and stereochemical considerations, and on the steric and electronic factors that determine the regiochemistry of the either kinetically or thermodynamically controlled hydrozirconation. The “Scope and Limitations” section presents information on functional group compatibilities and is organized by the type of synthetic transformation of alkenylzirconocenes. Representative applications of the hydrozirconation of alkynes are showcased in syntheses of natural products, comparisons to alternative methods for the hydrometallation of alkynes. The goal of this chapter is to demonstrate the significance of hydrozirconation in organic synthesis, including the utility of the stoichiometric zirconium organometallics obtained from alkyne substrates, and to provide inspiration for the future development of new synthetic methods and strategies.

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NMR of Organoselenium and Organotellurium Compounds

Panda

Singh

2012

Patai's Chemistry of Functional Groups

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This chapter gives a systematic account of and surveys the available data on 77 Se and 125 Te NMR spectra of organochalcogen compounds such as chacogenols, mono and dichalcogenides, chalcogenolates, tetra and hexa substituted chalcogen compounds, chalcogenyl halides, chalcogen‐containing heterocycles and macrocycles, chalcogen‐oxygen/nitrogen compounds, etc. The review is based on the literature from 1985 to 2011 and includes 780 references. The 77 Se/ 125 Te NMR spectra of organochalcogen compounds reveal expansive chemical shifts (δ Se /δ Te ) leading to sharp sensitivity of these nuclei (Se/Te) to their environment such as solvent, temperature, molecular geometry, ligand backbone, oxidation state, chelate ring size, steric strain, etc. This is well illustrated by the advantageous use of this spectroscopy in the successful determination of the solution state structure of several organochalcogen compounds. It is noted that the 125 Te and 77 Se chemical shifts of a large number of structurally similar organotellurium and selenium compounds show linear relationship.

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Conjugate addition of vinylic organocuprates generated via transmetalation of phenylseleno‐substituted vinylzirconates: Functionalization at the 4‐position of enones

Abstract: Hydrozirconation of propargylic selenides (1) or 4-phenylseleno-1-butyne (2) with

Cited by 6 publications

References 13 publications

A Stereoselective Approach to (Z)-1-Silyl-2-aryl-1,3-dienes from 4-(Phenylselanyl)but-1-yne via Palladium-Catalyzed Silylstannylation and Selenoxide Elimination

A Stereoselective Approach to (Z)-1-Silyl-2-aryl-1,3-dienes from 4-(Phenylselanyl)but-1-yne via Palladium-Catalyzed Silylstannylation and Selenoxide Elimination

Hydrozirconation of Alkynes

NMR of Organoselenium and Organotellurium Compounds

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