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1-(N-Acylamino)alkyltriarylphosphonium Salts with Weakened C_α-P⁺ Bond Strength-Synthetic Applications.

ABSTRACT: The α-amidoalkylating properties of 1-(N-acylamino)alkyltriarylphosphonium salts with weakened C_α-P⁺ bond strength are discussed and examined. It is demonstrated that such type of phosphonium salts reacts smoothly with a diverse array of carbon- and heteroatom-based nucleophiles, including 1-morpholinocyclohexene, 1,3-dicarbonyl compounds, benzotriazole sodium salt, p-toluenesulfinate sodium salt, benzylamine, triarylphosphines, and other P-nucleophiles. Reactions are conducted at room temperature, in a short time (5⁻15 min) and mostly without catalysts. Simple work-up procedures result in good or very good yields of products. The structures of known compounds were established by spectroscopic methods and all new compounds have been fully characterized using ¹H-, ¹³C-, ³¹P-NMR, IR spectroscopy, and high-resolution mass spectrometry. Mechanistic aspects of described transformations are also performed and discussed. It was demonstrated that unique properties make 1-(N-acylamino)alkyl-triarylphosphonium salts with weakened C_α-P⁺ bond strength interesting building blocks with great potential, especially in α-amidoalkylation reactions.

SUBMITTER: Adamek J

PROVIDER: S-EPMC6222910 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:The reactivity of the bis(pentalene)dititanium double-sandwich compound Ti2Pn†2 (1) (Pn† = 1,4-{SiiPr3}2C8H4) with CO2 is investigated in detail using spectroscopic, X-ray crystallographic, and computational studies. When the CO2 reaction is performed at -78 °C, the 1:1 adduct 4 is formed, and low-temperature spectroscopic measurements are consistent with a CO2 molecule bound symmetrically to the two Ti centers in a μ:η2,η2 binding mode, a structure also indicated by theory. Upon warming to room temperature the coordinated CO2 is quantitatively reduced over a period of minutes to give the bis(oxo)-bridged dimer 2 and the dicarbonyl complex 3. In situ NMR studies indicated that this decomposition proceeds in a stepwise process via monooxo (5) and monocarbonyl (7) double-sandwich complexes, which have been independently synthesized and structurally characterized. 5 is thermally unstable with respect to a μ-O dimer in which the Ti-Ti bond has been cleaved and one pentalene ligand binds in an η8 fashion to each of the formally TiIII centers. The molecular structure of 7 shows a "side-on" bound carbonyl ligand. Bonding of the double-sandwich species Ti2Pn2 (Pn = C8H6) to other fragments has been investigated by density functional theory calculations and fragment analysis, providing insight into the CO2 reaction pathway consistent with the experimentally observed intermediates. A key step in the proposed mechanism is disproportionation of a mono(oxo) di-TiIII species to yield di-TiII and di-TiIV products. 1 forms a structurally characterized, thermally stable CS2 adduct 8 that shows symmetrical binding to the Ti2 unit and supports the formulation of 4. The reaction of 1 with COS forms a thermally unstable complex 9 that undergoes scission to give mono(μ-S) mono(CO) species 10. Ph3PS is an effective sulfur transfer agent for 1, enabling the synthesis of mono(μ-S) complex 11 with a double-sandwich structure and bis(μ-S) dimer 12 in which the Ti-Ti bond has been cleaved.

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1-(N-Acylamino)alkyltriarylphosphonium Salts with Weakened C_α-P⁺ Bond Strength-Synthetic Applications.

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1-(N-Acylamino)alkyltriarylphosphonium Salts with Weakened Cα-P⁺ Bond Strength-Synthetic Applications.

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OmicsDI is part of the ELIXIR infrastructure

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1-(N-Acylamino)alkyltriarylphosphonium Salts with Weakened C_α-P⁺ Bond Strength-Synthetic Applications.