Regio- and Stereochemically Controlled Formation of Hydroxamic Acid Containinganti- orsyn-1,4-Cycloalkenols from Acylnitroso-Derived Diels−Alder Adducts

Surman,; Mj, Miller

doi:10.1021/jo010094a

Cited by 43 publications

(25 citation statements)

References 16 publications

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“…The regio and stereochemically controlled formation of hydroxamic acid containing anti-or syn-1,4-cycloalkenols was reported by M. J. Miller et al [27]. Treatment of acylnitroso hetero-Diels-Alder cycloadducts 48 with iron(III) or copper(II) in an alcohol solvent induces ring opening to afford predominantly monocyclic anti-1,4-hydroxamic acids 49.…”

Section: A Hetero-diels-alder Reactionmentioning

confidence: 81%

Synthesis of Acylnitroso Intermediates and Their Synthetic Applications

Iwasa¹,

Fakhruddin²,

Nishiyama³

2005

MROC

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Acylnitroso intermediates are usually known as super reactive species, always prepared in situ and can be readily trapped via hetero-Diels-Alder reactions with dienes or with olefins via ene reactions, which open a magnificent access to produce a variety of complicated and very demanding organic molecules. Both of these reactions of acylnitroso species have been proved as the key synthetic tool in the total synthesis of natural products. The synthetic methods used to prepare these intermediates as well as their recent synthetic applications to the total synthesis of natural products are briefly described in this minireview.

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Section: A Hetero-diels-alder Reactionmentioning

confidence: 81%

Synthesis of Acylnitroso Intermediates and Their Synthetic Applications

Iwasa¹,

Fakhruddin²,

Nishiyama³

2005

MROC

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“…The formation of 7 a – b may be rationalized by invoking a cyclopropane ring opening triggered by cleavage of the allylic CO bond (see below) 15g–h. Such cleavage is easy under polar conditions18 as shown by the formation of compounds 8 a – b during the cycloaddition between Boc‐nitroso and cycloheptatriene 4 a in CH 3 CN/H 2 O (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

Development of Domino Processes by Using 7‐Silylcycloheptatrienes and Its Analogues

Beniazza

Desvergnes

Girard

et al. 2012

Chemistry A European J

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7-Silyl- and 7-silylmethylcycloheptatrienes were shown to react with acylnitroso reagents at room temperature, through their norcaradiene forms, to generate the corresponding cycloadducts 5 a-b and 6 a-b as single diastereomers. The course of the reaction was dramatically modified by changing the reaction conditions. Using a polar medium, functionalized cyclohexa-1,3-dienes 7 a-b and bicyclic compounds 13 a-b were instead generated, incorporating one or two amino groups. Similar behavior was observed by using other dienophiles, including triazolinedione, but also activated aldehydes and ketones. A tentative mechanism has been proposed to rationalize the formation of both classes of products that relies on a domino process involving four consecutive elementary steps, in this order: 1) electrocyclic process, 2) hetero-Diels-Alder reaction, 3) cyclopropane ring opening, and 4) hetero-Diels-Alder reaction. Trapping of the cationic intermediate and isolation of the primary cycloadduct provide support for this hypothesis. An enantioselective version of the cascade using cycloheptatriene 4 b and aldehydes and ketones, under copper(II) catalysis was also carried out, leading to cyclohexa-1,3-dienes 21, 28, and 30 with enantioselectivities up to 93 % ee. Finally, elaboration of the intermediates above has been carried out, opening a straightforward access to sugar mimics 42-43 and complex polycyclic systems 36 and 39.

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“…The Miller research group reported that Lewis acids could mediate C À O bond cleavage of cycloadducts 91 and 92 in the presence of alcoholic solvents to afford hydroxamates 94-96 (Scheme 17). [109,110] Presumably, this transformation proceeded by coordination of the Lewis acid to the hydroxamate portion of the oxazine system through a structure similar to complex 93. The reaction was found to be moderately selective for 1,4-trans-hydroxamate 94 over 1,2-cis-hydroxamate 96.…”

Section: Cào Bond Cleavagementioning

confidence: 99%

The Nitrosocarbonyl Hetero‐Diels–Alder Reaction as a Useful Tool for Organic Syntheses

Bodnar¹,

2011

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Organic transformations that result in the formation of multiple covalent bonds within the same reaction are some of the most powerful tools in synthetic organic chemistry. Nitrosocarbonyl hetero-Diels–Alder (HDA) reactions allow for the simultaneous stereospecific introduction of carbon–nitrogen and carbon–oxygen bonds in one synthetic step, and provide direct access to 3,6-dihydro-1,2-oxazines. This Review describes the development of the nitrosocarbonyl HDA reaction and the utility of the resulting oxazine ring in the synthesis of a variety of important, biologically active molecules.

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Regio- and Stereochemically Controlled Formation of Hydroxamic Acid Containinganti- orsyn-1,4-Cycloalkenols from Acylnitroso-Derived Diels−Alder Adducts

Cited by 43 publications

References 16 publications

Synthesis of Acylnitroso Intermediates and Their Synthetic Applications

Synthesis of Acylnitroso Intermediates and Their Synthetic Applications

Development of Domino Processes by Using 7‐Silylcycloheptatrienes and Its Analogues

The Nitrosocarbonyl Hetero‐Diels–Alder Reaction as a Useful Tool for Organic Syntheses

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