Preparation of γ-Heterosubstituted Allylindium and Diindium Reagents and Their Reactions with Carbonyl Compounds

Hirashita, T.; Kamei, Toshiya; Horie, Tomoaki; Yamamura, Hisao; Kawai, Maki; Araki, Shuki

doi:10.1021/jo9816111

Cited by 41 publications

(30 citation statements)

References 17 publications

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“…[17] Curiously, only a few examples of gem-dimetallic allylic species have been hitherto described despite their high synthetic potentialities. Beside 5, other gem-homodimetallic allylic species such as other ditin [18] as well as dizinc [19] and more recently diindium compounds [20] have been described to date.…”

Section: Resultsmentioning

confidence: 99%

The Application of [γ‐(Silyloxy)allylidene]ditin to the Efficient Synthesis of the Chromophore of the Neocarzinostatin Dihydroxycyclopentene‐Based Dienediyne Core

Madec¹,

Férézou²

2005

Eur J Org Chem

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1‐(tert‐Butyldimethylsilyl)oxy‐3,3‐bis(tributylstannyl)propene (5), a versatile gem‐dimetallic allylic synthon accessible through various synthetic routes, has been condensed with (trimethylsilyl)propiolaldehyde to give the fully functionalised acyclic vinyltin compound 9h, which is a precursor of the complex dihydroxycyclopentene sub‐unit of neocarzinostatin chromophore (NCS) 1. Subsequent transformation into the geminal (E)‐α‐chloro‐(Z)‐α‐iodovinylic intermediate 20, followed by a palladium‐catalysed carbometallation/cyclisation reaction including in situ trapping with either (tributylstannyl)acetylene or the more functionalised 3,3‐diethoxy‐1‐(tributylstannyl)prop‐1‐yne delivered the corresponding alkyne‐substituted 4‐chloro‐1,2‐bis(silyloxy)cyclopent‐3‐enes 21 or 22, respectively. Chlorocyclopentene 21 was subsequently easily transformed into the target dienediyne adduct 23 by Sonogashira condensation with trimethylsilylacetylene. This diastereoselective process is efficient with only six steps and an overall 26 % yield from the allylic ditin precursor 5. More than just an NCS building block, the final acyclic dihydroxycyclopentene‐based dienediyne is also a seco analogue of the NCS chromophore. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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Section: Resultsmentioning

confidence: 99%

The Application of [γ‐(Silyloxy)allylidene]ditin to the Efficient Synthesis of the Chromophore of the Neocarzinostatin Dihydroxycyclopentene‐Based Dienediyne Core

Madec¹,

Férézou²

2005

Eur J Org Chem

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“…The RCM-elimination approaches outlined so far do not provide access to 2,5-disubstituted derivatives, but this can be achieved by altering the position of the leaving group (Scheme 8) [28]. Precursors 13 were prepared by sequential indium-mediated aldehyde allylation [35] and esterification. Takai-Utimoto olefination [36,37] then provided enol ether metathesis substrates 14.…”

Section: Synthesis Of Furans and Pyrroles By Rcm-elimination Sequencesmentioning

confidence: 99%

Synthesis of Heteroaromatic Compounds by Alkene and Enyne Metathesis

Race

Bower

2015

Topics in Heterocyclic Chemistry

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The development of robust and functional group tolerant metathesis catalysts has resulted in a rapid expansion of synthetic methodologies that employ this technology. In this chapter, alkene and enyne metathesis-based methodologies for the de novo construction of heteroaromatic compounds are discussed. These protocols capitalise upon the ability to generate complex olefinic products from the combination of two simpler precursors. Advancement to the heteroaromatic target can then be achieved either directly or after modification of the immediate metathesis product. Strategies that rely upon ring-closing alkene metathesis, ring-closing enyne metathesis and alkene cross-metathesis are outlined, along with applications in target-directed synthesis.

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“…[44] These alcohols were then transformed into esters using the corresponding acid chloride and a subsequent olefination under Takai-Utimoto conditions provided the desired enol ether 54.…”

Section: Conceptsmentioning

confidence: 99%

Ring‐Closing Metathesis: Novel Routes to Aromatic Heterocycles

Donohoe

Fishlock

Procopiou

2008

Chemistry A European J

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Olefin metathesis has been established as an important and general reaction in synthetic organic chemistry. Recently, it has attracted interest as a powerful tool for the construction of aromatic heterocycles. The importance of heteroaromatic motifs in medicinal chemistry and biology, as well as the efficiency and wealth of metathesis transformations, have resulted in significant success in this rapidly developing area.

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Preparation of γ-Heterosubstituted Allylindium and Diindium Reagents and Their Reactions with Carbonyl Compounds

Cited by 41 publications

References 17 publications

The Application of [γ‐(Silyloxy)allylidene]ditin to the Efficient Synthesis of the Chromophore of the Neocarzinostatin Dihydroxycyclopentene‐Based Dienediyne Core

The Application of [γ‐(Silyloxy)allylidene]ditin to the Efficient Synthesis of the Chromophore of the Neocarzinostatin Dihydroxycyclopentene‐Based Dienediyne Core

Synthesis of Heteroaromatic Compounds by Alkene and Enyne Metathesis

Ring‐Closing Metathesis: Novel Routes to Aromatic Heterocycles

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