Base-catalyzed addition of silylacetylenes to ketones: a route to protected tertiary propargyl alcohols

Kuciński, Krzysztof; Łuczak, Alicja; Mankouski, Aliaksei; Hreczycho, Grzegorz

doi:10.1039/d3qo00579h

Cited by 2 publications

(1 citation statement)

References 59 publications

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“…Then, this hypercoordinated species interact with second molecule of alkyne, yielding the desired product and acetylide ion along with the liberation of gaseous acetylene. Continued research within the Kuciński group has extended the application of BTMSA/KHMDS system to achieve the N ‐silylation of primary aromatic amines [219] and addition to ketones giving an access to protected propargyl alcohols [220] …”

Section: Synthesis Of 1‐silyl‐1‐alkynesmentioning

confidence: 99%

Synthesis of Alkynylsilanes: A Review of the State of the Art

Kuciński

2024

Adv Synth Catal

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This contribution offers a comprehensive overview of methods for forging sp C–Si bonds. Over time, alkynylsilanes (silylacetylenes), once considered mere byproducts of hydrosilylation processes, have become essential building blocks in organic synthesis. This literature review traces the evolution of their synthesis, from traditional methodologies relying on organolithium and organomagnesium compounds to more advanced cross‐coupling reactions involving hydro‐ and carbosilanes. Focused primarily on the past 25 years (2000‐2024), it also extensively references significant historical breakthroughs. By analyzing synthetic methodologies, the review not only offers a comprehensive survey of the current state of knowledge but also identifies areas for improvement. Furthermore, to emphasize the importance of 1‐alkynylsilanes (1‐silyl‐1‐alkynes), selected applications of these compounds are highlighted, confirming their significant potential in organic synthesis.

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Section: Synthesis Of 1‐silyl‐1‐alkynesmentioning

confidence: 99%

Synthesis of Alkynylsilanes: A Review of the State of the Art

Kuciński

2024

Adv Synth Catal

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Potassium Hexamethyldisilazide (KHMDS): Solvent-Dependent Solution Structures

Spivey,

Collum

2024

J. Am. Chem. Soc.

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Solution structures of potassium hexamethyldisilazide [KHMDS] and labeled [ 15 N]KHMDS were examined using a number of analytical methods including 29 Si NMR spectroscopy and density functional theory computations. A combination of 15 N− 29 Si couplings, 29 Si chemical shifts, and the method of continuous variations reveals dimers, monomers, and ion pairs. Weakly coordinating monofunctional ligands such as toluene, N,N-dimethylethylamine, and Et 3 N afford exclusively dimers. 1,3-Dioxolane, THF, dimethoxyethane, hexamethylphosphoramide, and diglyme provide dimers at low ligand concentrations and monomers at high ligand concentrations. N,N,N′,N'-Tetramethylethylenediamine and N,N,N′,N'-tetramethylcyclohexanediamine provide exclusively dimers at all ligand concentrations at ambient temperatures and significant monomer at −80 °C. Studies of 12-crown-4 ran into technical problems. Equimolar 15crown-5 forms a dimer, whereas excess 15-crown-5 affords a putative ion pair. Whereas equimolar 18-crown-6 also affords a dimer, an excess provides a monomer rather than a solvent-separated ion pair. [2.2.2]cryptand affords what is believed to be a contact-ionpaired cryptate. Solvation was probed using largely density functional theory (DFT) computations. Thermally corrected energies are consistent with lower aggregates and higher solvates at low temperatures, but the magnitudes of the computed temperature dependencies were substantially larger than the experimentally derived data.

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Base-catalyzed addition of silylacetylenes to ketones: a route to protected tertiary propargyl alcohols

Abstract: The base-catalyzed addition of alkynylsilanes to ketone derivatives enables the formation of various silyl-protected propargylic alcohols. Commercially available and inexpensive potassium bis(trimethylsilyl)amide (KHMDS) serves as an efficient transition metal-free catalyst...

Cited by 2 publications

References 59 publications

Synthesis of Alkynylsilanes: A Review of the State of the Art

Synthesis of Alkynylsilanes: A Review of the State of the Art

Potassium Hexamethyldisilazide (KHMDS): Solvent-Dependent Solution Structures

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