Alkynyliodonium salts in organic synthesis

Zhdankin, Viktor V.; Stang, Peter J.

doi:10.1016/s0040-4020(98)00410-4

Cited by 227 publications

(122 citation statements)

References 103 publications

Supporting

Mentioning

117

Contrasting

Unclassified

Order By: Relevance

“…[47] In 2013, Waser and Frei reported the alkynylation of thiols using TIPS-EBX (5) (Scheme 18). [49] The alkynylation reaction worked well for a broad range of substrates including phenolic, benzylic, heterocyclic, aliphatic, and peptidic thiols (products 89-92).…”

Section: C-n and C-o Bond Formationmentioning

confidence: 99%

Cyclic Hypervalent Iodine Reagents for Atom‐Transfer Reactions: Beyond Trifluoromethylation

et al. 2016

View full text Add to dashboard Cite

Hypervalent iodine compounds are privileged reagents in organic synthesis because of their exceptional reactivity. Among these compounds, cyclic derivatives stand apart because of their enhanced stability. They have been widely used as oxidants, but their potential for functional‐group transfer has only begun to be investigated recently. The use of benziodoxol(on)es for trifluoromethylation (Togni's reagents) is already widely recognized, but other transformations have also attracted strong interest recently. In this Review, the development in the area since 2011 will be presented. After a short summary of synthetic methods to prepare benziodoxol(on)e reagents, their use to construct carbon–heteroatom and carbon–carbon bonds will be presented. In particular, the introduction of alkynes by using ethynylbenziodoxol(on)e (EBX) reagents has been highly successful. Breakthroughs in the introduction of alkoxy, azido, difluoromethyl, and cyano groups will also be described.

show abstract

Section: C-n and C-o Bond Formationmentioning

confidence: 99%

Cyclic Hypervalent Iodine Reagents for Atom‐Transfer Reactions: Beyond Trifluoromethylation

et al. 2016

View full text Add to dashboard Cite

show abstract

“…Most works focus on only one class of phosphorus compounds, especially phosphonates. In this context, alkynyl iodonium salts have been long known as electrophilic alkynylation reagents, 11 but their use for the synthesis of alkynyl phosphorus compounds has been limited to phosphites 6b and phosphonates salts. 12 Our group has discovered and exploited the properties of cyclic alkynyl benziodoxolone reagents, such as TIPS-ethynylbenziodoxolone (TIPS-EBX, 6a) for the alkynylation of nucleophiles.…”

Section: Fig 1 Important Phosphorus-containing Bioactive Molecules (mentioning

confidence: 99%

“…A fast examination of base and reagent loading showed that 1.5 equivalents of DBU and 1.1 equivalents of TIPS-EBX 6a were optimal (entries 6-8). Other solvents gave lower yields when compared to THF (entries [9][10][11][12][13]. Alkynyl phosphite 7a was already formed within 3 min in 90% isolated yield (entry 14).…”

Section: Scheme 1 Our Approach Towards Phosphorus Alkynylationmentioning

confidence: 99%

Room temperature alkynylation of H-phosphi(na)tes and secondary phosphine oxides with ethynylbenziodoxolone (EBX) reagents

Chen

Waser

2014

Chem. Commun.

View full text Add to dashboard Cite

show abstract

“…For example, they can also be used in the synthesis of vinyliodonium salts, in cyclization reactions via carbene insertion or in cycloaddition reactions [16]. Several methods have been developed for their synthesis from different iodine precursors (Scheme 2.2).…”

Section: Alkynylation Using Alkynyliodonium Saltsmentioning

confidence: 99%

“…Key to obtain high enantioinduction with ketoester 46 was the use of benziodoxole 47 instead of benziodoxolone reagents. The obtained products could be easily cyclized 16 to the corresponding spiro compounds by iodination or selenenylation. Finally, Vesely and co-workers showed in 2013 that the asymmetric alkynylation of -nitro sulfone derivatives was also possible using cinchona-derived phase-transfer catalyst 50 (Scheme 2.15, C [113]).…”

Section: Scheme 213: Alkynylation Of Activated Ester Derivatives Witmentioning

confidence: 99%

Alkynylation with Hypervalent Iodine Reagents

Waser

2015

Hypervalent Iodine Chemistry

View full text Add to dashboard Cite

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.

show abstract

Alkynyliodonium salts in organic synthesis

Cited by 227 publications

References 103 publications

Cyclic Hypervalent Iodine Reagents for Atom‐Transfer Reactions: Beyond Trifluoromethylation

Cyclic Hypervalent Iodine Reagents for Atom‐Transfer Reactions: Beyond Trifluoromethylation

Room temperature alkynylation of H-phosphi(na)tes and secondary phosphine oxides with ethynylbenziodoxolone (EBX) reagents

Alkynylation with Hypervalent Iodine Reagents

Contact Info

Product

Resources

About