| 1. |
- Jalalian, Nazli, et al.
(author)
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Metal-Free Arylation of Oxygen Nucleophiles with Diaryliodonium Salts
- 2012
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In: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 18:44, s. 14140-14149
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Journal article (peer-reviewed)abstract
- Phenols and carboxylic acids are efficiently arylated with diaryliodonium salts. The reaction conditions are mild, metal free, and avoid the use of halogenated solvents, additives, and excess reagents. The products are obtained in good-to-excellent yields after short reaction times. Steric hindrance is very well tolerated, both in the nucleophile and diaryliodonium salt. The scope includes ortho-and halo-substituted products, which are difficult to obtain by metal-catalyzed protocols. Many functional groups are tolerated, including carbonyl groups, heteroatoms, and alkenes. Unsymmetric salts can be chemoselectively utilized to obtain products with hitherto unreported levels of steric congestion. The arylation has been extended to sulfonic acids, which can be converted to sulfonate esters by two different approaches. With recent advances in efficient synthetic procedures for diaryliodonium salts the reagents are now inexpensive and readily available. The iodoarene byproduct formed from the iodonium reagent can be recovered quantitatively and used to regenerate the diaryliodonium salt, which improves the atom economy.
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| 2. |
- Norrby, Per-Ola, 1962, et al.
(author)
-
α-Arylation by Rearrangement : On the Reaction of Enolates with Diaryliodonium Salts
- 2010
-
In: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 16:28, s. 8251-8254
-
Journal article (peer-reviewed)abstract
- Surprising equilibration: A new mechanism for the title reaction is supported by DFT calculations and experimental observations. The CI and OI intermediates are isoenergetic and equilibrate quickly. Thus, any chiral information induced in the initial complex will be destroyed. In the final CC bond-forming step, a [2,3]-rearrangement from the OI bonded intermediate is slightly preferred over the [1,2]-elimination from the CI bonded isomer (see scheme).
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| 3. |
- Petersen, Tue B., et al.
(author)
-
Metal-free synthesis of aryl esters from carboxylic acids and diaryliodonium salts
- 2011
-
In: Organic Letters. - : American Chemical Society (ACS). - 1523-7060 .- 1523-7052. ; 13:13, s. 3462-3465
-
Journal article (peer-reviewed)abstract
- An efficient arylation of carboxylic acids with diaryliodonium salts has been developed, giving aryl esters in high yields within short reaction times for both arom. and aliph. substrates. The transition-metal-free conditions are compatible with a range of functional groups, and good chemoselectivity is obsd. with unsym. diaryliodonium salts. Furthermore, steric hindrance in the ortho positions is well tolerated both in the carboxylic acid and in the diaryliodonium salt, yielding aryl esters that cannot be obtained via other esterification protocols.
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