Photolysis of nitrate esters. Photochemically initiated inversion of configuration

Binkley, Roger W.; Koholic, Dolores J.

doi:10.1021/jo01326a041

Cited by 26 publications

(4 citation statements)

References 2 publications

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“…Examination of models shows that this proton has a dihedral angle of ca. 90" to H.t] This agrees with the rationalisations for stereoselectivity in formation of [5,5] carbobicyclic compounds put forward by Curranlo and Rajanbabu. 1' In summary, tributyltin hydride induced cleavage of nitrate esters is followed by rapid fragmentation to form dioxolanyl radicals which undergo stereoselective cyclisations to form [5,S] and [S76]-fused dioxolanes.…”

supporting

confidence: 82%

“…Our first efforts at cyclisation were directed to the formation of [5,6] fused products using the substrates 14 + 17 (Scheme 4). These reactions are doubly challenging, since (i) the formation of six-membered rings is substantially slower than formation of five-membered rings allowing a greater opportunity for side rections to intervene, and (ii) attempts at cyclisations onto ester-containing side-chains to form five-or six-membered rings have frequently resulted in failure, as a result of the preference of the ester to adopt a trans R these methods to the synthesis of natural products featuring cyclic cis-vicinal diols.…”

mentioning

confidence: 99%

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Stereochemical control in cyclisation to bicyclic dioxolanes

Begley¹,

Fletcher²,

Murphy³

et al. 1993

J. Chem. Soc., Chem. Commun.

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Fragmentation of nitrate esters to yield dioxolanyl radicals has been followed by stereoselective cyclisation to bicyclic dioxolanes.Cyclisation of radicals 1 has been demonstrated1 to yield solely cis-fused 2. We wished to extend this stereoselective ringformation to dioxolanes and related heterocycles, and also to explore the formation of the corresponding [5,6] fused molecules. For this purpose, dioxolanyl radicals are required. To prepare precursors 3 in which Y = halogen would be very

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supporting

confidence: 82%

mentioning

confidence: 99%

Stereochemical control in cyclisation to bicyclic dioxolanes

Begley¹,

Fletcher²,

Murphy³

et al. 1993

J. Chem. Soc., Chem. Commun.

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“…The essential chemistry of our approach to the creation of hydroxyl-bearing siloxane-anchored SAMs is summarized in Scheme . The application of nitrate photolysis to hydroxyl formation has been reported by Binkley et al …”

Section: Resultsmentioning

confidence: 98%

Photocontrolled Formation of Hydroxyl-Bearing Monolayers and Multilayers

et al. 1996

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Siloxane-anchored, nitrate-bearing, monolayer films have been fabricated and have been used as the precursors for the photochemical creation of uniformly hydroxylated monolayer surfaces. The surface hydroxyl groups have been shown to be reactive toward phosphorylation and, more importantly, they can serve as the base layer for addition of a subsequent siloxane-anchored monolayer. This approach provides an important new tool for monolayer transformation and allows for photocontrol of organic multilayer construction.

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“…Most of these studies used excitation wavelengths >290 nm, a region of very weak absorption . For nitrate esters excited at λ>290 nm, photolysis involves cleavage of the O–NO 2 bond to form NO 2 and an alkoxy radical. − …”

Section: Introductionmentioning

confidence: 99%

UV Resonance Raman Investigation of Pentaerythritol Tetranitrate Solution Photochemistry and Photoproduct Hydrolysis

2017

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Ultraviolet resonance Raman spectroscopy (UVRR) is being developed for standoff trace explosives detection. To accomplish this, it is important to develop a deep understanding of the accompanying UV excited photochemistry of explosives, as well as the impact of reactions on the resulting photoproducts. In the work here we used 229 nm excited UVRR spectroscopy to monitor the photochemistry of pentaerythritol tetranitrate (PETN) in acetonitrile. We find that solutions of PETN in CDCN photodegrade with a quantum yield of 0.08 ± 0.02, as measured by high performance liquid chromatography (HPLC). The initial step in the 229 nm UV photolysis of PETN in CDCN is cleavage of an O-NO bond to form NO. The accompanying photoproduct is pentaerythritol trinitrate (PETriN), (CHONO)CCHOH formed by photolysis of a single O-NO. The resulting UVRR spectra show a dominant photoproduct band at ∼1308 cm, which derives from the symmetric stretch of dissolved NO. This photoproduct NO is hydrolyzed by trace amounts of water, which downshifts this 1308 cm NO Raman band due to the formation of molecular HNO. The dissociation of HNO to NO in the presence of additional water results in an intense NO- symmetric stretching UVRR band at 1044 cm.

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Photolysis of nitrate esters. Photochemically initiated inversion of configuration

Cited by 26 publications

References 2 publications

Stereochemical control in cyclisation to bicyclic dioxolanes

Stereochemical control in cyclisation to bicyclic dioxolanes

Photocontrolled Formation of Hydroxyl-Bearing Monolayers and Multilayers

UV Resonance Raman Investigation of Pentaerythritol Tetranitrate Solution Photochemistry and Photoproduct Hydrolysis

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