Phosphorus compounds. Part 68. Tetraphosphacubane chemistry: probing phosphorus reactivity by protonation, alkylation, and alkynylation. Formation of novel phosphonium di- and monocations in superacid media and monocations with super electrophiles

“…[46] This chemistry was also extended to tetraphosphacubane, which was alkynylated in 65-67 % yield (Scheme 26, b). [47] They also disclosed the reaction of bis(phenyliodonium)diyne triflates with triphenylphosphine, which gave bisphosphonium salts 150 and 151 in 94 % and 70 % yield, respectively (Scheme 26 c and d). [48]…”

Section: 4b Reactions With Alkynyliodonium Saltsmentioning

confidence: 98%

The Chemistry between Hypervalent Iodine(III) Reagents and Organophosphorus Compounds

2018

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The intersection between the chemistries of hypervalent iodine (HVI) reagents and organophosphorus compounds holds significant potential. To date, the merging of these research spheres has led to novel iodane motifs, many of which have been used in new oxyphosphorylation methodologies. In addition, HVI reagents have proven easily capable of transferring electrophilic carbon-based (alkyl, aryl, al-kynyl, etc.) ligands to various phosphorus nucleophiles. Furthermore, the ease with which HVI reagents oxidize phosphorus has led to novel esterification, amidation, alcohol functionalization and peptide coupling reactions. This Focus Review summarizes the chemistry to-date between these two important classes of compounds. Scheme 1. General reactivity modes of l 3 -iodanes.[a] Dr.Scheme 2. Phosphorus-containing HVI reagents.Scheme 3. ortho-Stabilized HVI reagents. Scheme 4. Phosphorus-containing HVI reagents generated in situ. Scheme 5. Synthesis of alkynyl phosphate esters. Scheme 6. Oxyphosphorylation of vinyliodonium salts. Scheme 10. Synthesis of a-carbonyl phosphonates and phosphinates. Scheme 11. Synthesis of a-carbonyl phosphonates. Scheme 12. Synthesis of a-carbonyl phosphonates via in situ-generated 26. Scheme 13. Synthesis of tris-ketol phosphates. Scheme 19. Phosphorylation of silylenol ethers. Scheme 20. Preparation of phosphonates by arylation of phosphites. Scheme 21. Arylation of PÀH phosphine oxides and phosphonates. Scheme 22. Synthesis of bis(triphenylphosphonium) salts. Scheme 23. Phosphorylation of alkynyliodonium salts with phosphites. Scheme 28. Synthesis of vinyl phosphonates from vinyl iodonium salts. Scheme 30. Trifluoromethylation of naphthyl-derived phosphines. Scheme 29. Trifluoromethylation of phosphines. Scheme 35. Peptide coupling mediated by PPh 3 and 200 or 217.Scheme 36. Synthesis of acyl and alkyl chlorides, and alkyl fluorides using 207 and 208 generated in situ.Scheme 37. Synthesis of mixed iodonium phosphonium ylides.

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“…In 1992, Stang and Critell showed that light irradia-9 tion was not needed if alkynyliodonium triflates were used [70]. Later, this methodology could be extended to other triaryl-or alkyl phosphines [71][72]. In 1990, Koser and Lodaya also reported the synthesis of alkynylphosphonates by the Arbusov reaction of alkynyliodonium tosylates with trialkyl phosphites (Scheme 2.7, B [73]).…”

Section: Alkynylation Of Phosphorus Sulfur and Other 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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Phosphorus compounds. Part 68. Tetraphosphacubane chemistry: probing phosphorus reactivity by protonation, alkylation, and alkynylation. Formation of novel phosphonium di- and monocations in superacid media and monocations with super electrophiles

Cited by 41 publications

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Tetraphosphatricyclo[4.2.0.0^2,5]octadienes; New Phosphaalkyne Cyclotetramers Derived from λ³σ²‐Diphosphetes

Tetraphosphatricyclo[4.2.0.0^2,5]octadienes; New Phosphaalkyne Cyclotetramers Derived from λ³σ²‐Diphosphetes

The Chemistry between Hypervalent Iodine(III) Reagents and Organophosphorus Compounds

Alkynylation with Hypervalent Iodine Reagents

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Phosphorus compounds. Part 68. Tetraphosphacubane chemistry: probing phosphorus reactivity by protonation, alkylation, and alkynylation. Formation of novel phosphonium di- and monocations in superacid media and monocations with super electrophiles

Cited by 41 publications

References 0 publications

Tetraphosphatricyclo[4.2.0.02,5]octadienes; New Phosphaalkyne Cyclotetramers Derived from λ3σ2‐Diphosphetes

Tetraphosphatricyclo[4.2.0.02,5]octadienes; New Phosphaalkyne Cyclotetramers Derived from λ3σ2‐Diphosphetes

The Chemistry between Hypervalent Iodine(III) Reagents and Organophosphorus Compounds

Alkynylation with Hypervalent Iodine Reagents

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Product

Resources

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Tetraphosphatricyclo[4.2.0.0^2,5]octadienes; New Phosphaalkyne Cyclotetramers Derived from λ³σ²‐Diphosphetes

Tetraphosphatricyclo[4.2.0.0^2,5]octadienes; New Phosphaalkyne Cyclotetramers Derived from λ³σ²‐Diphosphetes