Skeletal Rearrangements in the 2,3-Diazanorbornene Series. A Fast Access to Highly Functionalized Cyclopentanes

Bournaud, Chloée; Bonin, Martine; Micouin, Laurent

doi:10.1021/ol060972x

Cited by 31 publications

(24 citation statements)

References 18 publications

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“…Overall yield of the final product is around 50% with very good enantioselectivity (90% ee) (eq 8). 14 NH four steps NH Ph 50-60% overall yield 90% ee (8) Copper-catalyzed cycloaddition of organic azides and dimethyl phenyl aluminum acetylide affords 1,4-disubstituted-5-alumino-1,2,3-triazoles in good yields and with high regioselectivities (eq 9). 15 A new efficient synthesis of enantiomerically enriched cyclic 3-alkynylketones was achieved via the enantioselective conjugate addition of dimethyl phenyl aluminum acetylide onto α,βunsaturated ketones in the presence of Ni(II) complexes of bisphosphines as the catalyst (eq 10).…”

Section: Almentioning

confidence: 99%

Aluminum, Dimethyl(2-phenylethynyl) [Dimethyl Aluminum Phenyl Acetylide]

Kattamuri

Jiang

et al. 2012

Encyclopedia of Reagents for Organic Synthesis

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Section: Almentioning

confidence: 99%

Aluminum, Dimethyl(2-phenylethynyl) [Dimethyl Aluminum Phenyl Acetylide]

Kattamuri

Jiang

et al. 2012

Encyclopedia of Reagents for Organic Synthesis

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“…38 The protonation and acid-catalysed rearrangements of a tricyclo[4.2.2.2 2,5 ]dodeca-3,7,9,11-tetraene scaffold were studied. 47 Participation of the nitrogen lone pair is likely to stabilize the cation intermediate (50). The stereochemical course of the conversions is mainly determined by least motion chloride return in ion-pair intermediates.…”

Section: Cationic Rearrangementsmentioning

confidence: 99%

Molecular Rearrangements: Part 2. Other Reactions

Brandi

Gensini

2010

Organic Reaction Mechanisms · 2006

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The formation of α-phenyl-β-halovinyl cation, β-phenyl-α-halovinyl cation, and also the halogen-bridged and the spirocyclic phenyl-bridged cations, as intermediates of protonation of phenylethynyl halides, or of halogen addition to phenylethynes, has been evaluated by DFT at the B3LYP/6-31+G(d) level and, for comparison in representative cases, by B3LYP/6-311++G(d,p). 1 Structural and mechanistic studies of the lithium diisopropylamide (LDA)-mediated anionic Fries rearrangements of aryl carbamates have been described. 2 Substituents at the meta position of the arene (H, OMe, F) and the dialkylamino moiety of the carbamate (Me 2 N, Et 2 N, and i-Pr 2 N) markedly influence the relative rates of ortholithiation and subsequent Fries rearrangement. The mechanism of the Fries rearrangement of aryl formates promoted by boron trichloride has been studied by means of 1 H, 2 H, and 11 B NMR spectroscopy and DFT calculations. 3 After the formation of a 1:1 substrate -Lewis acid adduct, the rearrangement proceeds in two steps, beginning with the cleavage of the ester bond and the release of formyl chloride in situ, which, in turn, acts as a formylating agent, introducing 451

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“…The concluding stage involves nucleophilic substitution in the alkoxyphosphonium salt 6, leading to the acylation product RX and triphenylphosphine oxide. As a rule nucleophilic substitution is realized by an S N 2 mechanism with total inversion of the configuration at the asymmetric carbon atom of the alcohol molecule, although there are exceptions [9][10][11]. Inversion is not observed during anchimeric assistance from neighboring groups [11] or during the realization of a monomolecular nucleophilic substitution mechanism, e.g., during glycosylation [2].…”

Section: The General Characteristics and Certain Aspects Of The Mechamentioning

confidence: 99%

“…As a rule nucleophilic substitution is realized by an S N 2 mechanism with total inversion of the configuration at the asymmetric carbon atom of the alcohol molecule, although there are exceptions [9][10][11]. Inversion is not observed during anchimeric assistance from neighboring groups [11] or during the realization of a monomolecular nucleophilic substitution mechanism, e.g., during glycosylation [2]. In the absence of other nucleophilic reagents alkylation of the anion of diethyl hydrazinedicarboxylate (5) occurs, leading to the formation of the hydrazine 7.…”

Section: The General Characteristics and Certain Aspects Of The Mechamentioning

confidence: 99%

The Mitsunobu reaction in the chemistry of nitrogen-containing heterocyclic compounds. The formation of heterocyclic systems (review)

Голанцов

Карчава

Yurovskaya

2008

Chem Heterocycl Comp

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Methods for the design of nitrogen-containing heterocyclic systems involving the formation of C-N bonds under the conditions of the Mitsunobu reaction are discussed.The Mitsunobu reaction [1][2][3][4] is the reaction of compounds containing a mobile hydrogen atom HX with alcohols in the presence of a reagent system consisting of an azodicarboxylic ester and a phosphine PR 1 3 . This reaction results in the formation of an alkylation product RX accompanied by oxidation of the phosphine PR 1 3 to phosphine oxide R 1 3 P=O and reduction of the azodicarboxylic ester to the corresponding hydrazine.The reaction takes place under very mild conditions and usually at room temperature. If a chiral secondary alcohol ROH is used, the reaction is usually stereospecific and is accompanied by inversion of the configuration at the asymmetric carbon atom of the alcohol [1-3].From the moment of the first report [5] the Mitsunobu reaction became a powerful tool in synthetic organic chemistry and found widespread use in the synthesis of various heterocyclic compounds, optically active substances, steroids, alkaloids, carbohydrates, and nucleosides [1][2][3][4]6]. In particular, in a number of cases the Mitsunobu reaction has made it possible to synthesize new physiologically active compounds or to put forward new highly effective approaches to synthesis. Several reviews have been devoted to the Mitsunobu reaction [1-4, 6, 7]. Data on the use of the Mitsunobu reaction in the synthesis of alkaloids were reviewed in [6]. Various experimental techniques that make it possible to simplify the isolation of the products of the Mitsunobu reaction RX from the reaction mixture, including the use of reagents attached to a polymer support, were discussed in [7]. _______ * Dedicated to Afanasi Andreevich Akhrem on his 95th birthday. _________________________________________________________________________________________

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Skeletal Rearrangements in the 2,3-Diazanorbornene Series. A Fast Access to Highly Functionalized Cyclopentanes

Cited by 31 publications

References 18 publications

Aluminum, Dimethyl(2-phenylethynyl) [Dimethyl Aluminum Phenyl Acetylide]

Aluminum, Dimethyl(2-phenylethynyl) [Dimethyl Aluminum Phenyl Acetylide]

Molecular Rearrangements: Part 2. Other Reactions

The Mitsunobu reaction in the chemistry of nitrogen-containing heterocyclic compounds. The formation of heterocyclic systems (review)

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