Acetylenic esters. Preparation and mechanism of formation of alkynyl tosylates and mesylates via tricoordinate iodonium species

Stang, Peter J.; Surber, Bruce W.; Chen, Zhen Chu; Roberts, Kenneth A.; Anderson, Albert G.

doi:10.1021/ja00235a034

Cited by 117 publications

(40 citation statements)

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“…After evaporation and crystallization, alkynyl(phenyl)iodonium triflates 1 were obtained as crystals (eq 3). The results are given in the Table (entries [3][4][5][6]. As seen from the Table, the preparation of alkynyliodonium triflate 1a has been improved by using the PhI(OAc) 2 / Tf 2 O reagent system.…”

Section: An Alternative Synthesis Of Alkynyl(phenyl)iodonium Triflatementioning

confidence: 99%

An Alternative Synthesis of Alkynyl(phenyl)iodonium Triflates Using (Diacetoxyiodo)benzene and Alkynylsilanes

Kitamura¹,

Kotani²,

Fujiwara³

1998

Synthesis

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Section: An Alternative Synthesis Of Alkynyl(phenyl)iodonium Triflatementioning

confidence: 99%

An Alternative Synthesis of Alkynyl(phenyl)iodonium Triflates Using (Diacetoxyiodo)benzene and Alkynylsilanes

Kitamura¹,

Kotani²,

Fujiwara³

1998

Synthesis

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“…In 1987, Stang and co-workers reported that alkynyliodonium tosylates can be converted to the corresponding ynol tosylates in the presence of copper triflate (Scheme 2.5, A [51,52]). The rearrangement of alkynyliodonium carboxylates is even easier and occurs spontaneously in absence of any catalyst (Scheme 2.5, B [53,54]).…”

Section: Alkynylation Of Oxygen and Nitrogen Nucleophilesmentioning

confidence: 99%

Alkynylation with Hypervalent Iodine Reagents

Waser

2015

Topics in Current Chemistry

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Alkynes are among the most versatile functional groups in organic synthesis. They are also frequently used in chemical biology and materials science. Whereas alkynes are traditionally added as nucleophiles into organic molecules, hypervalent iodine reagents offer a unique opportunity for the development of electrophilic alkyne synthons. Since 1985, alkynyliodonium salts have been intensively used for the alkynylation of nucleophiles, in particular soft carbon nucleophiles and heteroatoms. They have made especially a strong impact in the synthesis of highly useful ynamides. Nevertheless, their use has been limited by their instability. Since 2009, more stable ethynylbenziodoxol(on)e (EBX) reagents have been discovered as superior electrophilic alkyne synthons in many transformations. They can be used for the alkynylation of acidic C-H bonds with bases or aromatic C-H bonds using transition metal catalysts. They were also highly successful for the functionalization of radicals or transition metal-catalyzed domino processes. Finally, they allowed the alkynylation of a further range of heteroatom nucleophiles, especially thiols, under exceptionally mild conditions. With these recent discoveries, hypervalent iodine reagents have definitively demonstrated their utility for the efficient synthesis of alkynes based on non-classical disconnections.

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“…Although this early work had serious limitations,108 it galvanized the field. Improvements rapidly followed so that by the mid-1980's a variety of alkynyl(phenyl)iodonium salts were readily available as stable microcrystalline compounds 112,113…”

Section: Independent Careermentioning

confidence: 99%

“…We prepared these unique esters by interaction of alkynyl(phenyl)iodonium triflates with ArCO 2 Na for the carboxylate esters,145 40 , CuOTf or AgOTf for the sulfonate esters,112a,b 41 , and (R′O) 2 P(O)ONa for the phosphate esters,146 42 , as shown in Scheme 9. X-ray structure determination of the carboxylate ester,147 40 , and the sulfonate ester,148 41 , established, as anticipated, that the C sp –O bond is considerably shorter than the C sp2 –O bond of ordinary esters with a value of 1.366 Å vs 1.445 Å for carboxylate esters and 1.331 Å vs. 1.465 Å for the sulfonate esters respectively 147,148…”

Section: Independent Careermentioning

confidence: 99%

From Solvolysis to Self-Assembly

Stang

2008

J. Org. Chem.

Self Cite

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My sojourn from classical physical-organic chemistry and solvolysis to self-assembly and supramolecular chemistry, over the last forty years, is described. My contributions to unsaturated reactive intermediates, namely vinyl cations and unsaturated carbenes, along with my decade long involvement with polyvalent iodine chemistry, especially alkynyliodonium salts, as well as my more recent research with metal-ligand, coordination driven and directed self-assembly of finite supramolecular ensembles are discussed.

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Acetylenic esters. Preparation and mechanism of formation of alkynyl tosylates and mesylates via tricoordinate iodonium species

Cited by 117 publications

References 0 publications

An Alternative Synthesis of Alkynyl(phenyl)iodonium Triflates Using (Diacetoxyiodo)benzene and Alkynylsilanes

An Alternative Synthesis of Alkynyl(phenyl)iodonium Triflates Using (Diacetoxyiodo)benzene and Alkynylsilanes

Alkynylation with Hypervalent Iodine Reagents

From Solvolysis to Self-Assembly

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