Recent advances in sulfur- and phosphorous-centered radical reactions for the formation of S–C and P–C bonds

Pan, Xiangqiang; Zou, Jian‐Ping; Yi, Wen‐Bin; Zhang, Wei

doi:10.1016/j.tet.2015.04.117

Cited by 163 publications

(58 citation statements)

References 335 publications

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“…Generally, classical synthetic strategies for the formation of CAP bond are largely rely on the use of transition-metal-catalyzed cross-coupling processes [7][8][9]. In the past few years, the addition of P-centered radicals to arenes or other unsaturated functionalities opened a new avenue for the construction of CAP bond [10,11]. However, the formation of Pcentered radicals in those processes generally needs to use transition-metal salts or oxidants at high reaction temperature.…”

Section: Introductionmentioning

confidence: 99%

Visible light-mediated C P bond formation reactions

2019

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Section: Introductionmentioning

confidence: 99%

Visible light-mediated C P bond formation reactions

2019

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“…The reaction of phosphorus-centered radicals is well-established and has many synthetic applications, summarized in several reviews [28,51,52]. Because phosphorus can exist in different oxidation states, it is possible to generate phosphinyl, phosphinoyl, or phosphonyl radicals.…”

Section: Addition Of Phosphorus-centered Radicalsmentioning

confidence: 99%

“…Subsequent addition to alkenes can initiate efficient chain reactions by hydrogen atom abstraction (thiol-ene reaction) or polymerizations. Indeed, the application of thiyl radicals in organic synthesis [52,57] or polymer chemistry [58] has been reviewed extensively. Even thio sugars are suitable radical precursors, and have been used for cyclizations and additions to other unsaturated carbohydrates at various positions [59,60] Therefore, this mini-review will focus only on the additions of sulfur-centered radicals to endo-glycals.…”

Section: Addition Of Sulfur-centered Radicalsmentioning

confidence: 99%

Addition of Heteroatom Radicals to endo-Glycals †

Linker

2020

Chemistry

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Radical reactions have found many applications in carbohydrate chemistry, especially in the construction of carbon–carbon bonds. The formation of carbon–heteroatom bonds has been less intensively studied. This mini-review will summarize the efforts to add heteroatom radicals to unsaturated carbohydrates like endo-glycals. Starting from early examples, developed more than 50 years ago, the importance of such reactions for carbohydrate chemistry and recent applications will be discussed. After a short introduction, the mini-review is divided in sub-chapters according to the heteroatoms halogen, nitrogen, phosphorus, and sulfur. The mechanisms of radical generation by chemical or photochemical processes and the subsequent reactions of the radicals at the 1-position will be discussed. This mini-review cannot cover all aspects of heteroatom-centered radicals in carbohydrate chemistry, but should provide an overview of the various strategies and future perspectives.

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“…For a long time, radical reactions, especially chain reactions, were considered as unsuitable for synthetic purposes because of their low selectivity. Currently, the interest to radical mechanisms in organic synthesis increases substantially . It has been found that some reactions, which were not considered earlier as reactions with participation of radicals, are in fact radical reactions in disguise.…”

Section: Introductionmentioning

confidence: 99%

Dichloromethane as solvent and reagent: a case study of photoinduced reactions in mixed phosphonium‐iodonium ylide

Левина

Klimovich

Vinogradov

et al. 2018

J of Physical Organic Chem

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Several years ago the photoinduced reaction of mixed phosphonium-iodonium ylides (1) with acetylenes (2) to give λ 5 -phosphinolines (3) and substituted furans (4) was described. This reaction is one-pot, metal-free synthesis of heterocycles 3 and 4 with the yields of 40% to 80%. The reaction proceeds only in dichloromethane (DCM) at the high ylide concentrations (>0.01 mol/L). The product analysis by 31 P NMR, electrospray ionization mass spectrometry, UVvis spectrophotometry, and the dynamic light scattering study of the self-aggregation of the ylide in DCM showed a dual role of the solvent in the photoinduced reactions of mixed phosphonium-iodonium ylide: (i) at the low ylide concentrations (<0.01 mol/L), the conjugated photoinitiation of the chain reaction in DCM results in the formation of chlorine-containing products and (ii) at the high ylide concentrations (>0.01 mol/L), the photolysis mechanism is determined by self-organization of the ylide molecules to give large stable aggregates in DCM, in which the target heterocycles are synthesized. Two important issues follow from the study. First, the annulation reaction between mixed phosphonium-iodonium ylide and acetylenes occurs only when the reactive intermediates are in close proximity to one other, and, second, DCM is not inert reagent in reactions occurring with participation of radicals and in one form or another can participate in photoinduced radical reactions of various solutes.KEYWORDS annulation with acetylenes, dichloromethane, phosphonium-iodonium ylides, radical reactions, selfassembly This article is dedicated with respect and affection to the memory of the late Prof. Nikolay S. Zefirov.

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Recent advances in sulfur- and phosphorous-centered radical reactions for the formation of S–C and P–C bonds

Cited by 163 publications

References 335 publications

Visible light-mediated C P bond formation reactions

Visible light-mediated C P bond formation reactions

Addition of Heteroatom Radicals to endo-Glycals †

Dichloromethane as solvent and reagent: a case study of photoinduced reactions in mixed phosphonium‐iodonium ylide

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