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Review
. 2018 May 30:14:1263-1280.
doi: 10.3762/bjoc.14.108. eCollection 2018.

Atom-economical group-transfer reactions with hypervalent iodine compounds

Andreas Boelke  1 , Peter Finkbeiner  1 , Boris J Nachtsheim  1
Affiliations
Review

Atom-economical group-transfer reactions with hypervalent iodine compounds

Andreas Boelke et al. Beilstein J Org Chem. .

Abstract

Hypervalent iodine compounds, in particular aryl-λ3-iodanes, have been used extensively as electrophilic group-transfer reagents. Even though these compounds are superior substrates in terms of reactivity and stability, their utilization is accompanied by stoichiometric amounts of an aryl iodide as waste. This highly nonpolar side product can be tedious to separate from the desired target molecules and significantly reduces the overall atom efficiency of these transformations. In this short review, we want to give a brief summary of recently developed methods, in which this arising former waste is used as an additional reagent in cascade transformations to generate multiple substituted products in one step and with high atom efficiency.

Keywords: atom economy; benziodoxolones; homogeneous catalysis; hypervalent iodine; iodonium salts.

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Figures

Scheme 1
Scheme 1
Overview of different types of iodane-based group-transfer reactions and their atom economy based on the molecular mass of the corresponding λ3-iodane.
Scheme 2
Scheme 2
(a) Structure of diaryliodonium salts 1. (b) Diarylation of a suitable substrate A with one equivalent of diaryliodonium salt 1.
Scheme 3
Scheme 3
Synthesis of biphenyls 3 and 3’ with symmetrical diaryliodonium salts 1.
Scheme 4
Scheme 4
Synthesis of diaryl thioethers 5.
Scheme 5
Scheme 5
Synthesis of two distinct S-aryl dithiocarbamates 7 and 7’ from one equivalent of diaryliodonium salt 1.
Scheme 6
Scheme 6
Synthesis of substituted isoindolin-1-ones 9 from 2-formylbenzonitrile 8 and the postulated reaction mechanism.
Scheme 7
Scheme 7
Domino C-/N-arylation of indoles 10.
Scheme 8
Scheme 8
Domino modification of N-heterocycles 12 via in situ-generated directing groups.
Scheme 9
Scheme 9
Synthesis of triarylamines 17 through a double arylation of anilines.
Scheme 10
Scheme 10
Selective conversion of novel aryl(imidazolyl)iodonium salts 1b to 1,5-disubstituted imidazoles 18.
Scheme 11
Scheme 11
Selected examples for the application of cyclic diaryliodonium salts 19.
Scheme 12
Scheme 12
Tandem oxidation–arylation sequence with (dicarboxyiodo)benzenes 20.
Scheme 13
Scheme 13
Oxidative α-arylation via the transfer of an intact 2-iodoaryl group.
Scheme 14
Scheme 14
Tandem ortho-iodination/O-arylation cascade with PIDA derivatives 20b.
Scheme 15
Scheme 15
Synthesis of meta-N,N-diarylaminophenols 28 and the postulated mechanism.
Scheme 16
Scheme 16
(Dicarboxyiodo)benzene-mediated metal-catalysed C–H amination and arylation.
Scheme 17
Scheme 17
Postulated mechanism for the amination–arylation sequence.
Scheme 18
Scheme 18
Auto-amination and cross-coupling of PIDA derivatives 20c.
Scheme 19
Scheme 19
Tandem C(sp3)–H olefination/C(sp2)–H arylation.
Scheme 20
Scheme 20
Atom efficient functionalisations with benziodoxolones 36.
Scheme 21
Scheme 21
Atom-efficient synthesis of furans 39 from benziodoxolones 36a and their further derivatisations.
Scheme 22
Scheme 22
Oxyalkynylation of diazo compounds 42.
Scheme 23
Scheme 23
Enantioselective oxyalkynylation of diazo compounds 42’.
Scheme 24
Scheme 24
Iron-catalysed oxyazidation of enamides 45.
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