β-Elimination of a Phosphonate Group from an Alkoxy Radical:  An Intramolecular Acylation Approach Using an Acylphosphonate as a Carbonyl Group Acceptor

Kim, Sunggak; Cho, Chang Ho; Lim, Chae Jo

doi:10.1021/ja036499p

Cited by 39 publications

(19 citation statements)

References 22 publications

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“…This reaction represents the first example of a phosphono iodocyclization onto a C-C triple bond ( Figure 65) Conformationally constrained a-Boc-aminophosphonates (387), (388) (389), (390) and (391) were made via a transition metal catalysed Curtius rearrangement. 184 Arylphosphonic acids (422) have been discovered to react with a variety of alkenes in the presence of Pd(OAc) 2 and Me 3 NO providing Heck-type adducts (423). 171 A two step synthesis of 2-oxo-2-vinyl-1,3,2-dioxaphospholanes and dioxaphosphorinane (392) involves transesterification of diethyl phosphite with selected diols followed by palladium catalysed coupling of the resultant cyclic phosphites (393) with vinyl bromide (Figure 67).…”

Section: Halogenoalkyl and Halogenocycloalkyl Acidsmentioning

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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Section: Halogenoalkyl and Halogenocycloalkyl Acidsmentioning

confidence: 99%

Organophosphorus Chemistry

Hall

Bricklebank

Grampel³

et al. 2006

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“…It has been shown that phosphinyl radical additions are reversible. [18] Radicals derived from phosphinates have been exploited for the preparation of aromatic compounds, [19] and phosphonyl radical eliminations for the synthesis of ketones, [20] although in both cases the systems were significantly biased to favor the elimination pathway. The first case was a rearomatization, and the second involved a highly reactive acyl phosphonate, with restoration of a C=O bond.…”

mentioning

confidence: 99%

Titanium‐Mediated Domino Radical Cyclization/β Elimination of Phosphine Oxides

et al. 2004

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“…Among these new carbonyl radical acceptors, the acyl phosphonate stood out in terms of reactivity. 85 Experiments employing the use of iodo alkenyl acyl derivatives…”

Section: Scheme 42 Effect Of Phenylthio-and Phenylseleno-radical Leamentioning

confidence: 99%

“…As mentioned in the first part of this chapter, there are numerous reports pertaining to either ionic and radical synthesis of ketones. [73][74][75][76][77][78][79][80][81][82][83][84][85] In particularly, 1,5diketones are valuable synthetic starters in the synthesis of fused-ring systems which form the carbon backbone of many interesting classes of compounds such as alkaloids, steroids and terpenes. 86 In addition, 1,5-diketones pave an easy route to functionalized pyridines.…”

Section: Proposed Strategy Of Radical-mediated Synthesis Of 15diketomentioning

confidence: 99%

“…This was in stark contrast to the other functionalized carbon-centered radicals that had found success with the same protocol previously. 85 Various other systems for the generation of the α-keto radicals, in particularly, tin-free initiator systems such as azo initiators like AIBN and also the combined use of triethylborane and air which were known to generate the reactive ethyl radical that was required to propagate the radical chain effectively 32a (Table 4, Entries 2 and 3). Unfortunately, these methods failed to give the desired 1,5-diketone and reduction was a predominant observation even under these reactions (Table 4).…”

Section: α-mentioning

confidence: 99%

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