Enantioselective Cyclization of Alkene Radical Cations

Crich, David; Shirai, Michio; Rumthao, Sochanchingwung

doi:10.1021/ol035564x

Cited by 36 publications

(15 citation statements)

References 18 publications

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“…In a similar manner, the oxidation of an electron-rich olefin leads to an electrophilic radical cation intermediate. , The result is an opportunity to develop new modes of reactivity. Consider the generalized transformations outlined in Scheme (refs − , for related nonelectrochemical reactions please see refs − and − ). In the scheme, the normal reactivity of an electron-rich olefin is compared to that of the corresponding oxidation reaction.…”

Section: Intramolecular Anodic Olefin Coupling Reactionsmentioning

confidence: 99%

Using Physical Organic Chemistry To Shape the Course of Electrochemical Reactions

2018

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While organic electrochemistry can look quite different to a chemist not familiar with the technique, the reactions are at their core organic reactions. As such, they are developed and optimized using the same physical organic chemistry principles employed during the development of any other organic reaction. Certainly, the electron transfer that triggers the reactions can require a consideration of new "wrinkles" to those principles, but those considerations are typically minimal relative to the more traditional approaches needed to manipulate the pathways available to the reactive intermediates formed downstream of that electron transfer. In this review, three very different synthetic challenges-the generation and trapping of radical cations, the development of site-selective reactions on microelectrode arrays, and the optimization of current in a paired electrolysis-are used to illustrate this point.

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Section: Intramolecular Anodic Olefin Coupling Reactionsmentioning

confidence: 99%

Using Physical Organic Chemistry To Shape the Course of Electrochemical Reactions

2018

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“…A promising extension of this methodology arises from the nature of the contact radical ion pair generated during fragmentation. 26 These species have short lifetimes before undergoing recombination. If nucleophilic attack of the amine is to compete with this process then it implies a high degree of pre-organisation and the possibility of stereocontrol.…”

Section: General Radical Methodologymentioning

confidence: 99%

3 Synthetic methods : Part (i) Free-radical reactions

Rowlands

2004

Annu. Rep. Prog. Chem., Sect. B: Org. Chem.

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The following short review covers some highlights of the use of radical reactions in the field of organic chemistry during 2003. It is intended to be illustrative of recent advances in radical chemistry rather than all-inclusive, thus much elegant work reported this year is not described here. Highlights include the continued move away from tin reagents; prominent this year has been the development of phosphorus-based strategies. [1][2][3][4] Stereoselectivity is playing an increasingly important role in radical chemistry with four groups reporting enantiopure hydride sources, 1,5-7 a number of excellent auxiliary controlled additions 8-10 and the first example of catalytic enantioselective radical generation. 11 Scheme 1

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“…24 The most efficient method for the synthesis of racemic plasmenylcholines (52), an important class of glycerophospholipids, requires only six steps beginning from the inexpensive starting materials solketal or glycerol and acrolein. 27 (R)-and (S)-enantiomers of novel lysophosphatidylcholine analogues (59) and (60) have been synthesized from commercially available L-and D-serine as starting materials by a short and efficient method (Scheme 10). 25 A series of phospholipid analogues (53)- (56) have been prepared and evaluated for their water solubility and inhibition of PLC BC .…”

Section: Phosphoric Acids and Their Derivativesmentioning

confidence: 99%

“…The results described provide a foundation for understanding both the bonding behavior of monosubstituted phosphates and the electrostatic environment of the phosphoryl group, including that within enzyme active sites. 60 The diastereoselective synthesis of an optically pure spiroketal (113) via an intramolecular tandem hydrogen abstraction reaction, promoted by an alkoxy radical, has been reported (Scheme 30). 51 Non-coordinating amino H-bond donors adjacent to a zinc (II)center enhance the affinity of phosphates to the zinc (II) center (Scheme 25).…”

Section: Scheme 13mentioning

confidence: 99%

Organophosphorus Chemistry

Hall

Bricklebank

Grampel³

et al. 2006

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Organophosphorus compounds are ubiquitous in nature, and due to their innate chemical properties, serve a fundamental role in a number of important fields. Among the more prominent features that elevate their status as a unique and versatile class of compounds, include variable oxidation states, multivalency, asymmetry and metal-binding properties. Their presence in bioactive natural products, endogenous biomolecules, small molecule therapeutic agents and pro-drugs substantiates their role in modern synthetic chemistry and chemical biology. Moreover, their central use as ligands and effectors in asymmetric catalysis, as well as key functional groups for the development of new synthetic methods, has taken the field to new heights. This Thematic Series highlights and details some of the novel methods that are advancing the field of organophosphorus chemistry.The Thematic Series covers topics that range from new synthetic methods and phosphorus-based ligands in asymmetric catalysis to bisphosphonates as promising enzyme inhibitors. More specifically, the Thematic Series spans new methods in C-P bond formation, chiral phosphines in nucleophilic organocatalysis, chiral N-phosphinyl auxiliaries, cyclic phosphonamide reagents in the total synthesis of natural products, phosphinate-containing heterocycles, new routes to phosphinoyl-indoles and phosphinoyl-isocoumarins and new chemistries of H-phosphonates. The Thematic Series also details work on new metathesis-based reactions of vinyl phosphonates and phosphate tethers, novel phosphorus-based ligands in asymmetric catalysis, novel rasta resin-triphenylphosphine oxides and their use as recyclable heterogeneous reagents, the Atherton-Todd reaction, cyclic phosphonium ionic liquids with distinct properties, photo-removable phosphate protecting groups, new methods of C-H functionalization using phosphoryl-related directing groups, the exciting chemistry of substituted phosphanylidenecarbenes and phosphoryl azides, and bisphosphonate ethers as promising inhibitors of geranylgeranyl diphosphate synthase (GGDPS).The articles and reviews capture the emerging potential of organophosphorus compounds and exciting opportunities in the field, and hopefully, will inspire and motivate investigators in the field to investigate new chemistry in this area. Taken collectively, organophosphorus chemistry embodies a broad, vibrant and continual growing scientific area with this Thematic Series highlighting recent advances in the field. We are grateful and indebted to the authors for their hard work and exciting contri-

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Enantioselective Cyclization of Alkene Radical Cations

Cited by 36 publications

References 18 publications

Using Physical Organic Chemistry To Shape the Course of Electrochemical Reactions

Using Physical Organic Chemistry To Shape the Course of Electrochemical Reactions

3 Synthetic methods : Part (i) Free-radical reactions

Organophosphorus Chemistry

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