Novel synthesis of long-chain primary alkyl compounds

Gibson, Thomas; Tulich, Linda

doi:10.1021/jo00322a015

Cited by 41 publications

(12 citation statements)

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“…The development of strong colour changes accompanying decomposition is also common, 35,[53][54][55] as we have observed in this study (red in toluene, purple in thf ). Deep red or crimson coloration appears to be characteristic of Zr(III) formation in these reactions.…”

Section: Olefin Eliminationsupporting

confidence: 71%

Insertion and isomerisation of internal olefins at alkylaluminium hydride: catalysis with zirconocene dichloride

Weliange¹,

McGuinness²,

Gardiner³

et al. 2015

Dalton Trans.

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The insertion of internal olefins (hydroalumination) and chain walking isomerisation at di-n-octylaluminium hydride [Al(Oct)2H], promoted by zirconocene dichloride [Cp2ZrCl2] has been studied. The reaction between [Cp2ZrCl2] and [Al(Oct)2H] in non-polar solvents leads to clusters containing bridging hydride ligands between Zr and Al. This system promotes hydroalumination of 1-octene but is largely ineffective for internal octenes (2-, 3-, 4-octene). In tetrahydrofuran the Zr-Al hydride clusters formed are more reactive and catalyse insertion and isomerisation of internal olefins to primary metal-alkyls, although this is accompanied by catalyst deactivation. Elimination and removal of 1-octene from the system post insertion/isomerisation was attempted, but it was found that the presence of the Zr catalyst leads to back-isomerisation to internal octenes, along with further decomposition with n-octane formation. Some possible pathways of catalyst decomposition, involving reduction of Zr and alkane elimination, have been studied theoretically.

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Section: Olefin Eliminationsupporting

confidence: 71%

Insertion and isomerisation of internal olefins at alkylaluminium hydride: catalysis with zirconocene dichloride

Weliange¹,

McGuinness²,

Gardiner³

et al. 2015

Dalton Trans.

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“…We found that treating 2 with a mixture of Cp 2 ZrCl 2 and Red-Al 38 (22 and 23). Alternatively, addition of TMSCN and I 2 provided nheptadecanonitrile 24 in 75% yield.…”

Section: Main Textmentioning

confidence: 96%

Selective Terminal Functionalization of Linear Alkanes

Marek

Bruffaerts

Buhnik-Rosenblau

et al. 2021

Preprint

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Selective undirected functionalization of strong primary C-H bonds of linear alkanes, that do not possess directing groups, historically stands as one of the most challenging transformation in chemistry. In this Article, we report a two-step sequential strategy involving a biocatalytic dehydrogenation / remote hydrofunctionalization, as a unified and versatile approach to selectively convert linear alkanes into a large array of valuable functionalized aliphatic derivatives. The dehydrogenation is carried out by a mutant strain of Rhodococcus and the produced alkenes are subsequently engaged in a remote functionalization through a metal-catalyzed hydrometalation/migration sequence that subsequently react with a large variety of electrophiles. The judicious implementation of this combined biocatalytic and organometallic approach enabled us to develop a high-yielding protocol to site-selectively functionalize unreactive primary C–H bonds.

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“…It is probable that the inner ether linkage may be rationalized in terms of 'Pd-catalyzed redox-relay,' 29,30 by which there is migration of an unsaturated alkene bond to create another vinyl ether linkage at the internal ether linkage. The iterative process of b-hydride elimination and migratory insertion is catalyzed by palladium reagents; this is similar to the action of Zr, 31 Fe, 32 and Ru 33 reagents. In the present case, we speculate that the 1-hydroxy sugar derivative is released first; this is then followed by the relay reaction to create a vinyl ether linkage at the inner site and then the release of the original tag 1 (Scheme 4).…”

Section: Attachment and Detachment Of Carbohydrate Derivative On The mentioning

confidence: 99%

A recyclable heavy fluorous tag carrying an allyl alcohol pendant group: design and evaluation toward applications in synthetic carbohydrate chemistry

Fukuda

Tojino

Goto

et al. 2015

Carbohydrate Research

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Novel synthesis of long-chain primary alkyl compounds

Cited by 41 publications

References 0 publications

Insertion and isomerisation of internal olefins at alkylaluminium hydride: catalysis with zirconocene dichloride

Insertion and isomerisation of internal olefins at alkylaluminium hydride: catalysis with zirconocene dichloride

Selective Terminal Functionalization of Linear Alkanes

A recyclable heavy fluorous tag carrying an allyl alcohol pendant group: design and evaluation toward applications in synthetic carbohydrate chemistry

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