Photooxygenation of vinylstannanes: tin-substituted allylic hydroperoxides through the regio- and diastereoselective ene reaction with singlet oxygen

Adam, Waldemar; Klug, P.

doi:10.1021/jo00064a035

Cited by 24 publications

(5 citation statements)

References 1 publication

Supporting

Mentioning

Contrasting

Order By: Relevance

“…It is also worth mentioning that the 1 O 2 ene reaction with vinyl silanes 92 and stannanes 93 exhibited a high degree of geminal selectivity with respect to the silyl of stannyl groups, respectively. Although steric factors might be responsible for the geminal selectivity, the selectivity was mainly attributed to electronic factors.…”

Section: Methodsmentioning

confidence: 97%

Recent Mechanistic Insights in the Singlet Oxygen Ene Reaction

Alberti¹,

Orfanopoulos²

2010

Synlett

View full text Add to dashboard Cite

Singlet oxygen reacts with alkenes, which bear allylic hydrogens, in an ene fashion to afford allylic hydroperoxides. This reaction, apart from its synthetic usefulness, has received extensive mechanistic attention. Numerous experimental studies (e.g., trapping of intermediates, deuterium kinetic isotope effects, regio-or stereoselectivity studies etc.) and to a lesser extend computational work, support a stepwise mechanism with the formation of a threemembered ring (perepoxide-like) intermediate. This Account mainly highlights our group's earlier and recent experimental efforts to ascertain facts relating to this concept.

show abstract

Section: Methodsmentioning

confidence: 97%

Recent Mechanistic Insights in the Singlet Oxygen Ene Reaction

Alberti¹,

Orfanopoulos²

2010

Synlett

View full text Add to dashboard Cite

show abstract

“…The ene reaction of singlet oxygen ( 1 O 2 ) with alkenes, the so-called Schenck reaction, constitutes a convenient route to allylic hydroperoxides . Much work has been carried out in recent years on such photooxygenations, particularly on its diastereo- and regioselectivity. − The prominent controlling factor for the regioselectivity in the Schenck reaction 2 is the by now classical cis effect, but more recently, gem -directing 5 and “nonbonding large group” interactions have been recognized …”

Section: Introductionmentioning

confidence: 99%

Diastereoselective Singlet Oxygen Ene Reaction (Schenck Reaction) and Diastereoselective Epoxidations of Heteroatom-Substituted Acyclic Chiral Olefins: A Mechanistic Comparison

et al. 1996

Self Cite

View full text Add to dashboard Cite

The directing propensity of allylic and homoallylic heteroatom substituents on the diastereoselective singlet oxygen ene reaction (Schenck reaction) of acyclic, chiral olefins has been investigated. These extensive stereochemical results offer evidence for our proposed mechanism of the diastereoselective singlet oxygen ene reaction. Thus, provided a substrate possesses sufficient 1,3-allylic strain to populate preferentially the appropriate conformation, the photooxygenation is directed threo-selectively by intramolecular hydrogen bonding in the threo-A exciplex of allylic alcohols, while electron-accepting or bulky substituents result in the erythro-configurated products. A detailed comparison of the diastereoselectivities for the singlet oxygen ene reaction with those of the epoxidation by m-chlorobenzoic acid (mCPBA) and dioxirane of several judiciously chosen substrates showed that both oxygen transfer processes are influenced similarly by allylic and homoallylic substituents. Thus, it is shown that the acyclic, allylic alcohol 1a is epoxidized highly threo-selectively by methyl(trifluoromethyl)dioxirane due to hydrogen bonding in the transition state and that bulky and/or electron-accepting substituents direct all three oxidants erythro-selectively. These pronounced steering effects on the diastereoselectivity of oxygen transfer processes (photooxygenation and epoxidation) should be valuable for the rational design of stereocontrolled oxyfunctionalizations by 1O2, mCPBA, and dioxiranes.

show abstract

“…Remarkable high geminal selectivity was also observed in 1 O 2 ene reactions with vinyl silanes (65,132,134–136) and stannanes (137). In this case, although steric factors contribute to the observed geminal selectivity, it was mostly assigned to electronic aspects.…”

Section: Chemistrymentioning

confidence: 85%

Singlet Oxygen: Discovery, Chemistry, C₆₀‐Sensitization^†

Orfanopoulos

2021

Photochem & Photobiology

View full text Add to dashboard Cite

This review article refers to the discovery of excited molecular oxygen, in particular on its lower singlet excited state ( 1 D g , 1 O 2 ). After a short report on singlet oxygen generation, the review is focused on the chemistry of this reactive species. Specifically, the three major reactions of 1 O 2 with unsaturated organic substrates, namely the [4 + 2] and [2 +2] cycloadditions as well as the ene reaction, are reviewed. The proposed mechanisms of these reactions, through the years, based on experimental and computational work, have been presented. Selected examples of singlet oxygen-synthetic applications are also mentioned. The [60]fullerene and fullereno-materials photosensitized oxidations in homogeneous, as well as in heterogeneous conditions, are also comprehensively discussed.Finally, the self-sensitized photooxidation of open cage fullerenes as well as fullerenes bearing oxidizable groups is reported.

show abstract

Photooxygenation of vinylstannanes: tin-substituted allylic hydroperoxides through the regio- and diastereoselective ene reaction with singlet oxygen

Cited by 24 publications

References 1 publication

Recent Mechanistic Insights in the Singlet Oxygen Ene Reaction

Recent Mechanistic Insights in the Singlet Oxygen Ene Reaction

Diastereoselective Singlet Oxygen Ene Reaction (Schenck Reaction) and Diastereoselective Epoxidations of Heteroatom-Substituted Acyclic Chiral Olefins: A Mechanistic Comparison

Singlet Oxygen: Discovery, Chemistry, C₆₀‐Sensitization^†

Contact Info

Product

Resources

About

Photooxygenation of vinylstannanes: tin-substituted allylic hydroperoxides through the regio- and diastereoselective ene reaction with singlet oxygen

Cited by 24 publications

References 1 publication

Recent Mechanistic Insights in the Singlet Oxygen Ene Reaction

Recent Mechanistic Insights in the Singlet Oxygen Ene Reaction

Diastereoselective Singlet Oxygen Ene Reaction (Schenck Reaction) and Diastereoselective Epoxidations of Heteroatom-Substituted Acyclic Chiral Olefins: A Mechanistic Comparison

Singlet Oxygen: Discovery, Chemistry, C60‐Sensitization†

Contact Info

Product

Resources

About

Singlet Oxygen: Discovery, Chemistry, C₆₀‐Sensitization^†