Metal-Free Highly Regioselective Aminotrifluoroacetoxylation of Alkenes

Lovick, Helena M.; Michael, Forrest E.

doi:10.1021/ja906648w

Cited by 167 publications

(82 citation statements)

References 15 publications

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“…By contrast, the two-component heteroarylation of olefins bearing tethered O-or N-nucleophiles did not proceed to afford the expected tetrahydrofurans or pyrrolidines: in the case of 4-penten-1-ol, a complex mixture of products was obtained, whilst N-(4-pentenyl)tosylamide furnished a 9:1 mixture of piperidine 15 and pyrrolidine 16 (Scheme 2, bottom). Although the essential role of gold in related aminooxygenations has been demonstrated under basic conditions, [32] we found that, as expected under acidic conditions, [33] the formation of 15 and 16 proceeded equally efficiently in the absence of gold. [25] In all cases, the oxyarylation products were accompanied by alkyl 2-iodobenzoates, formed in situ from the IBA-de- …”

Section: Scope-monosubstituted Olefinssupporting

confidence: 60%

Gold‐Catalysed Oxyarylation of Styrenes and Mono‐ and gem‐Disubstituted Olefins Facilitated by an Iodine(III) Oxidant

Ball

Lloyd‐Jones

Russell

2012

Chemistry A European J

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1-Hydroxy-1,2-benziodoxol-3(1H)-one (IBA) is an efficient terminal oxidant for gold-catalysed, three-component oxyarylation reactions. The use of this iodine(III) reagent expands the scope of oxyarylation to include styrenes and gem-disubstituted olefins, substrates that are incompatible with the previously reported Selectfluor-based methodology. Diverse arylsilane coupling partners can be employed, and in benzotrifluoride, homocoupling is substantially reduced. In addition, the IBA-derived co-products can be recovered and recycled.

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Section: Scope-monosubstituted Olefinssupporting

confidence: 60%

Gold‐Catalysed Oxyarylation of Styrenes and Mono‐ and gem‐Disubstituted Olefins Facilitated by an Iodine(III) Oxidant

Ball

Lloyd‐Jones

Russell

2012

Chemistry A European J

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“…[64] While the degree of diastereo-and regioselectivity are substrate dependent, this reaction is notable as it reports the first example of the direct oxyamination of homoallylic amines to exhibit both 6-endo and anti selectivity regarding addition across the alkene geometry, see 99 a to 100 a.…”

Section: Metal-free Oxidation Protocolsmentioning

confidence: 99%

“…This unusual endo selectivity was exploited in the concise, stereoselective synthesis of (À)-pseudoconhydrine. [64] Iodine(V) reagents: Iodine(V) has also been used to effect the direct oxyamination of olefins by Nicolaou et al [65] In this procedure, the exposure of N-arylamides 101 to DessMartin periodinane (DMP) delivered iso-imidoquinone intermediates 102, which underwent [4 + 2] Diels-Alder reactions with a range of electron-rich alkenes to afford the desired 2-amilides 103 (Scheme 43). [66] This methodology was applied in the core synthesis of various complex natural products such as elisabethin A and pseudopterosin A (Figure 3).…”

Section: Metal-free Oxidation Protocolsmentioning

confidence: 99%

Recent Developments in Methodology for the Direct Oxyamination of Olefins

Donohoe

Callens

Flores

et al. 2010

Chemistry A European J

262

116

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1,2-Amino alcohols are high-value, versatile functional groups that are found in scores of biologically active molecules and other interesting synthetic targets such as ligands and auxiliaries. Given their prominent position within organic compounds of import, it is no surprise to note that many routes have been developed to access this motif and there are many different starting points from which a synthetic chemist might embark on a synthesis. However, one particular approach stands out from the others, and this is the direct conversion of an alkene to a vicinal amino alcohol derivative (oxyamination). Research in this field has been particularly active in recent years and many interesting new methodologies have been reported. The purpose of this review is to give the reader a tour of the methods that have emerged in the last few years so one can appreciate the myriad of different metals and reagents that can accomplish the oxyamination of alkenes. There are still many challenges to be overcome and, herein, we also outline the areas that are ripe for further development and which bode well for the future.

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“…One possible reason for this is the lack of suitable carbon electrophiles that can activate the carbon-carbon double bond of the allylic amide. [14,15] To the best of our knowledge, there are no examples of such a catalytic electrophilic carbofunctionalization of this class of molecules. Despite these advances, the development of novel methods that catalytically generate carbon electrophiles capable of activating alkenes to nucleophilic attack remains a challenge; the solution to this challenge would be of significant use in complex molecule synthesis.…”

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confidence: 99%

Copper‐Catalyzed Intramolecular Electrophilic Carbofunctionalization of Allylic Amides

2013

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Allylic amides and their derivatives represent a versatile class of nitrogen-containing building blocks, the bifunctional nature of which has enabled a diverse array of transformations and established them as strategically important molecules in chemical synthesis. [1,2] Particularly useful are reactions where an electrophile activates the carbon-carbon double bond towards attack of the pendant oxygen atom of the amide carbonyl group to form either a five or sixmembered ring heterocycle, depending on the mode of cyclization (Scheme 1 a). [3] Most of these reactions are triggered by heteroatom electrophiles, often activated by a catalyst, and result in the formation of a carbon-oxygen and a carbon-heteroatom bond. It is, however, surprising that the related electrophilic carbofunctionalization process is rare. One possible reason for this is the lack of suitable carbon electrophiles that can activate the carbon-carbon double bond of the allylic amide. The development of Pd-catalyzed oxyarylation and aminoarylation reactions, in particular by Wolfe and co-workers, [4] as well as related Pd, [5] Cu, [6] and Aucatalyzed [7] processes have provided an alternative approach to related alkene difunctionalization [8] and can be applied to derivatives of the generic allylic amine framework. Despite these advances, the development of novel methods that catalytically generate carbon electrophiles capable of activating alkenes to nucleophilic attack remains a challenge; the solution to this challenge would be of significant use in complex molecule synthesis.As part of an overarching program aimed at the exploitation of high oxidation state metal species we, [9] and others, [10] have established that the combination of copper catalysts and diaryliodonium salts gives rise to a high oxidation state Cu III / aryl [11] intermediate that displays reactivity of an aromatic electrophile (Scheme 1 b). We reasoned that this distinct catalytic activation strategy could be used to generate the aromatic electrophile equivalent that would be needed to affect an intramolecular oxyarylation of allylic amides, thus complementing the corresponding heteroatom electrophile triggered cyclizations that have become a mainstay in synthesis.We selected aryl-substituted allylic amides with which to test our copper-catalyzed oxyarylation strategy as the products would generate a broadly useful class of diarylated amino alcohols. Furthermore, we noted that some aryl-substituted allylic amides have been utilized in other electrophile triggered cyclization reactions. For example, treatment with acid induces an intramolecular hydration-type reaction to form the 6-membered-ring oxazine product (Scheme 1 c). [13] Similarly, treatment with bromine gives rise to a bromocyclization, again forming the oxazine product, although this is dependent on the geometry of the starting alkene and the electronic nature of the aromatic ring. [14,15] To the best of our knowledge, there are no examples of such a catalytic electrophilic carbofunctionalization of this class of ...

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Metal-Free Highly Regioselective Aminotrifluoroacetoxylation of Alkenes

Cited by 167 publications

References 15 publications

Gold‐Catalysed Oxyarylation of Styrenes and Mono‐ and gem‐Disubstituted Olefins Facilitated by an Iodine(III) Oxidant

Gold‐Catalysed Oxyarylation of Styrenes and Mono‐ and gem‐Disubstituted Olefins Facilitated by an Iodine(III) Oxidant

Recent Developments in Methodology for the Direct Oxyamination of Olefins

Copper‐Catalyzed Intramolecular Electrophilic Carbofunctionalization of Allylic Amides

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