Gaining Absolute Control of the Regiochemistry in the Cobalt-Catalyzed 1,4-Hydrovinylation Reaction

Arndt, Marion; Dindaroğlu, Mehmet; Schmalz, Hans‐Günther; Hilt, Gerhard

doi:10.1021/ol202696n

Cited by 69 publications

(31 citation statements)

References 44 publications

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“…4 When cobalt catalysts are applied in the 1,4-hydrovinylation reaction, the proposed active catalyst [Co(dppe) + ] exhibits excellent regioselectivity for the carbon−carbon bond formation at the α-carbon atom of the terminal alkene while a similar cobalt complex utilizing a more complex bidentate phosphine−phosphite ligand (SchmalzPhos) forms the new carbon−carbon bond with high selectivity at the β-carbon. 9 The advantage of the one-pot sequence presented here is exemplified by the variability of the coupling partners. For example, the replacement of DMB with the unsymmetrical 2-(trimethylsilyloxy)buta-1,3-diene (TMSO-diene) led to completely different types of products.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Multidirectional Cobalt-Catalyzed Diels–Alder/1,4-Hydrovinylation Sequences

2012

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The combination of two powerful cobalt-catalyzed carbon-carbon bond forming transformations, namely, the Diels-Alder and the 1,4-hydrovinylation reaction, in a tandem or a sequential one-pot procedure, opened up a concise and efficient route to polysubstituted aromatic systems and cyclohex-3-enone derivatives. Furthermore, ozonolysis of the latter products led to polycarbonyl compounds with tailored carbonyl group distances which could be characterized via their respective BF(2)-borinane complexes. The cobalt catalysts tolerated several functional groups, and a flexible approach to polyfunctionalized compounds in concise fashion was described.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Multidirectional Cobalt-Catalyzed Diels–Alder/1,4-Hydrovinylation Sequences

2012

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“…[37] Scheme 30. In this respect, Hilt recently reported the inversion of the regiochemistry for the carboncarbon bond formation for the donor component when a ligand developed by Schmalz was applied.…”

Section: 4-hydrovinylationmentioning

confidence: 99%

Hydrovinylation Reactions – Atom‐Economic Transformations with Steadily Increasing Synthetic Potential

Hilt

2012

Eur J Org Chem

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107

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The intermolecular carbon–carbon bond formation between two alkenes also known as 1,2‐hydrovinylation reaction can be realised with different transition metal catalysts. The application of styrene derivatives, norbornenes and other alkenes in asymmetric catalysis with a variety of chiral ligands leads to α‐chiral alkene products in an atom‐economic transformation. Accordingly, the 1,2‐hydrovinylation is one of just a few asymmetric transformations which produce stereogenic centres in the absence of polarised functional groups. The 1,4‐hydrovinylation of terminal alkenes and 1,3‐dienes can be controlled by the electronic nature of the alkene starting material for the selective formation of linear or branched 1,4‐dienes. These adducts can be used for the synthesis of 1,3‐ as well as 1,4‐dicarbonyl derivatives upon ozonolysis of suitable intermediates. As an extension of the 1,4‐hydrovinylation reaction a cobalt‐catalysed 1,4‐hydrobutadienylation reaction is reported where two different 1,3‐dienes react selectively for the formation of 1,3,6‐trienes.

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“…The 1,2‐hydrovinylation of the alkyne does not allow the formation of a stereogenic centre, but the newly formed 1,3‐diene is highly substituted and is not accepted by the catalyst as starting material for another transformation. Less substituted 1,3‐dienes were applied as a different source of a π system by Hilt and co‐workers in cobalt‐catalysed 1,4‐hydrovinylation reactions with terminal alkenes to generate 1,4‐dienes 3. In these reactions no homo‐hydrovinylation was observed and in addition to the previous reaction the regioselectivity for the formation of the 1,4‐diene products, 7 or 8 , can be controlled by the choice of ligand system [1,2‐bis(diphenylphosphino)ethane (dppe) or L1 ] on the cobalt catalyst (Scheme ).…”

Section: Methodsmentioning

confidence: 99%