Hypervalent iodine reagent-mediated reactions involving rearrangement processes

2020 ◽  
Vol 56 (91) ◽  
pp. 14119-14136
Author(s):  
Beibei Zhang ◽  
Xiaoxian Li ◽  
Boying Guo ◽  
Yunfei Du
Keyword(s):  
Claisen Rearrangement ◽  
Beckmann Rearrangement ◽  
Hypervalent Iodine ◽  
Ring Contraction ◽  
Hofmann Rearrangement ◽  
Rearrangement Processes

We summarize the developments of hypervalent iodine reagents-mediated reactions involving [1,2]-migration, Hofmann rearrangement, Beckmann rearrangement, ring contraction/expansion, [3,3]-sigmatropic/iodonium-Claisen rearrangement and some miscellaneous rearrangements.

Hypervalent Iodine-Mediated Beckmann Rearrangement of Ketoximes

Synlett ◽  
2018 ◽  
Vol 29 (11) ◽  
pp. 1465-1468 ◽  
Author(s):  
Tomohiro Maegawa ◽  
Yasuyoshi Miki ◽  
Ryohei Oishi ◽  
Kazutoshi Segi ◽  
Hiromi Hamamoto ◽  
...  
Keyword(s):  
Lewis Acid ◽  
Beckmann Rearrangement ◽  
Hypervalent Iodine ◽  
Mild Conditions ◽  
High Yields

We developed a Beckmann rearrangement employing hypervalent iodine reagent under mild conditions. The reaction of ketoxime with hypervalent iodine afforded the corresponding ketone, but premixing of hypervalent iodine and a Lewis acid was effective for promoting Beckmann rearrangement. Aromatic and aliphatic ketoximes were converted into their corresponding amides in good to high yields.

Hofmann Rearrangement of Carboxamides Mediated by Hypervalent Iodine Species Generated in Situ from Iodobenzene and Oxone: Reaction Scope and Limitations

2010 ◽  
Vol 12 (20) ◽  
pp. 4644-4647 ◽  
Author(s):  
Aleksandra A. Zagulyaeva ◽  
Christopher T. Banek ◽  
Mekhman S. Yusubov ◽  
Viktor V. Zhdankin
Keyword(s):  
Hypervalent Iodine ◽  
Hofmann Rearrangement ◽  
Iodine Species

Asparagine-selective cleavage of peptide bonds through hypervalent iodine-mediated Hofmann rearrangement in neutral aqueous solution

2014 ◽  
Vol 5 (7) ◽  
pp. 2747 ◽  
Author(s):  
Kana Tanabe ◽  
Atsuhiko Taniguchi ◽  
Takuya Matsumoto ◽  
Kounosuke Oisaki ◽  
Youhei Sohma ◽  
...  
Keyword(s):  
Aqueous Solution ◽  
Hypervalent Iodine ◽  
Peptide Bonds ◽  
Hofmann Rearrangement ◽  
Neutral Aqueous Solution

Functional Group Interconversion

2015 ◽  
Author(s):  
Tristan H. Lambert
Keyword(s):  
Lone Pair ◽  
Hypervalent Iodine ◽  
Hofmann Rearrangement ◽  
Nitrogen Lone Pair ◽  
University Of Bristol ◽  
The University ◽  
Peptide Acids ◽  
Photochemical Cleavage ◽  
Sterically Induced ◽  
Direct Amidation

Chaozhong Li of the Shanghai Institute of Organic Chemistry reported (J. Am. Chem. Soc. 2012, 134, 10401) the silver nitrate catalyzed decarboxylative fluorination of carboxylic acids, which shows interesting chemoselectivity in substrates such as 1. A related decarboxylative chlorination was also reported by Li (J. Am. Chem. Soc. 2012, 134, 4258). Masahito Ochiai at the University of Tokushima has developed (Chem. Commun. 2012, 48, 982) an iodobenzene-catalyzed Hofmann rearrangement (e.g., 3 to 4) that proceeds via hypervalent iodine intermediates. The dehydrating agent T3P (propylphosphonic anhydride), an increasingly popular reagent for acylation chemistry, has been used (Tetrahedron Lett. 2012, 53, 1406) by Vommina Sureshbabu at Bangalore University to convert amino or peptide acids such as 5 to the corresponding thioacids with sodium sulfide. Jianqing Li and co-workers at Bristol-Myers Squibb have shown (Org. Lett. 2012, 14, 214) that trimethylaluminum, which has long been known to effect the direct amidation of esters, can also achieve the direct coupling of acids and amines, such as in the preparation of amide 8. The propensity of severely hindered 2,2,6,6-tetramethylpiperidine (TMP) amides such as 9 to undergo solvolysis at room temperature has been shown (Angew. Chem. Int. Ed. 2012, 51, 548) by Guy Lloyd-Jones and Kevin Booker-Milburn at the University of Bristol. The reaction proceeds by way of the ketene and is enabled by sterically induced destabilization of the usual conformation that allows conjugation of the nitrogen lone pair with the carbonyl. Matthias Beller at Universität Rostock has found (Angew. Chem. Int. Ed. 2012, 51, 3905) that primary amides may be transamidated via copper(II) catalysis. The conditions are mild enough that an epimerization-prone amide such as 11 undergoes no observable racemization during conversion to amide 13. A photochemical transamidation has been achieved (Chem. Sci. 2012, 3, 405) by Christian Bochet at the University of Fribourg that utilizes 385-nm light to activate a dinitroindoline amide in the presence of amines such as 15, which produces the amide 16. Notably, photochemical cleavage of the Ddz protecting group occurs at a shorter wavelength of 300 nm.

Hypervalent-Iodine-Mediated Ring-Contraction Monofluorination Affording Monofluorinated Five-Membered Ring-Fused Oxazolines

2017 ◽  
Vol 19 (19) ◽  
pp. 5300-5303 ◽  
Author(s):  
Yong-Chao Han ◽  
Yan-Dong Zhang ◽  
Qun Jia ◽  
Jian Cui ◽  
Chi Zhang
Keyword(s):  
Membered Ring ◽  
Hypervalent Iodine ◽  
Ring Contraction

Hypervalent-iodine induced quasi-Favorskii C-ring contraction of 12-oxosteroids: A shortcut to C-norsteroids

Steroids ◽  
2013 ◽  
Vol 78 (2) ◽  
pp. 234-240 ◽  
Author(s):  
Jacqueline Sánchez-Flores ◽  
Vanessa G. Pelayo-González ◽  
Margarita Romero-Ávila ◽  
Blas Flores-Pérez ◽  
Marcos Flores-Álamo ◽  
...  
Keyword(s):  
Hypervalent Iodine ◽  
Ring Contraction

Hypervalent Iodine Catalyzed Hofmann Rearrangement of Carboxamides Using Oxone as Terminal Oxidant

2012 ◽  
Vol 77 (24) ◽  
pp. 11399-11404 ◽  
Author(s):  
Akira Yoshimura ◽  
Kyle R. Middleton ◽  
Matthew W. Luedtke ◽  
Chenjie Zhu ◽  
Viktor V. Zhdankin
Keyword(s):  
Hypervalent Iodine ◽  
Hofmann Rearrangement
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