Rhodium(II)-Catalyzed Stereoselective Synthesis of Allylsilanes

Guptill, David M.; Cohen, Carolyn M.; Davies, Huw M. L.

doi:10.1021/ol4028978

Cited by 16 publications

(12 citation statements)

References 29 publications

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“…Davies reported that a-allylsilanes or a-benzylsilanes can be obtained with high enantiomeric purity from the Rh II -(S)-N-[p-(dodecylphenyl)sulfonyl]prolinate catalyzed decomposition of avinyl-a-diazomethanes or a-phenyl-a-diazomethanes in the presence of PhMe2SiH. 28,29 In this work, the Rh II -prolinate catalyzed decomposition of methyl a-phenyl-a-diazoacetate in the presence of PhMe2SiH in dichloromethane resulted in the formation of abenzylsilane in a very low ee (3%). Using pentane as the solvent at room temperature resulted in the formation of the product in 36% ee.…”

Section: Scheme 5 Asymmetric Insertion Reaction Of Rh II -Carbenes Inmentioning

confidence: 99%

Recent progress in the catalytic carbene insertion reactions into the silicon–hydrogen bond

2017

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The following review will explore the historical development of Si-H bond insertion reactions, giving an up-to-date account on the metal catalysts often employed, in addition to an assessment of their strengths and weaknesses. Diazo compounds have great synthetic potential as versatile reagents for the formation of metal carbenes, allowing the selective formation of C-C and C-heteroatom bonds and thus the introduction of functional groups into organic molecules. C-Si bond-forming methods, that introduce silicon motifs into organic molecules, rely on catalysts derived from metals such as rhodium, copper, iridium, silver, ruthenium, and iron to achieve the desired activities and selectivities.

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Section: Scheme 5 Asymmetric Insertion Reaction Of Rh II -Carbenes Inmentioning

confidence: 99%

Recent progress in the catalytic carbene insertion reactions into the silicon–hydrogen bond

2017

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“…Previously, we had shown that the TMSE esters are prone to intramolecular reactions, 27 but we anticipated that this ester functionality would be compatible with intermolecular reactions of reactive alkenes. The TCE group appears to be very robust for rhodium carbene reactions, and so we expected donor/acceptor carbenes bearingTCE ester acceptor group would be very effective in intermolecular cyclopropanations.…”

Section: Introduction1mentioning

confidence: 98%

Enantioselective dirhodium(II)-catalyzed cyclopropanations with trimethylsilylethyl and trichloroethyl aryldiazoacetates

et al. 2015

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Highly functionalized cyclopropanecarboxylates were readily prepared by rhodium-catalyzed cyclopropanation of alkenes with aryldiazoacetates and styryldiazoaceates, in which the ester functionality is either trimethylsilylethyl (TMSE) or trichlorethyl (TCE). By having labile protecting groups on the ester, chiral triarylcyclopropane carboxylate ligands were conveniently prepared. The asymmetric induction during cyclopropanation is dependent on the nature of the ester group and the chiral dirhodium tetracarboxylate catalyst. The prolinate catalyst Rh2(S-DOSP)4 was the optimum catalyst for asymmetric intermolecular cyclopropanation of TMSE diazoesters with styrene, while Rh2(R-BPCP)4 was the optimum catalyst for TCE diazoesters.

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“…Indeed, cyclohexylallene reacted with secondary silanes Ph 2 SiH 2 and MePhSiH 2 , in the presence of 1 mol% Co(acac) 2 and 1 mol % xantphos, affording the corresponding ( Z )-allylsilanes 1b and 1c in high yields with excellent stereoselectivities (Fig. 2b, c ) 11 . In addition, we tested a nitrogen-based ligand mes PDI for this transformation, and the reaction afforded a mixture of ( Z )- 1a , ( E )- 1a and ( E )- 1a with low regio- and stereoselectivity (Table 1 , entry 10).…”

Section: Resultsmentioning

confidence: 98%

Access to stereodefined (Z)-allylsilanes and (Z)-allylic alcohols via cobalt-catalyzed regioselective hydrosilylation of allenes

Wang

Teo

2017

Nat Commun

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Hydrosilylation of allenes is the addition of a hydrogen atom and a silyl group to a carbon–carbon double bond of an allene molecule and represents a straightforward and atom-economical approach to prepare synthetically versatile allylsilanes and vinylsilanes. However, this reaction generally produces six possible isomeric organosilanes, and the biggest challenge in developing this reaction is to control both regioselectivity and stereoselectivity. The majorities of the developed allene hydrosilylation reactions show high selectivity towards the production of vinylsilanes or branched allylsilanes. By employing a cobalt catalyst generated from readily available and bench-stable cobalt precursor and phosphine-based ligands, here we show that this reaction proceeds under mild conditions in a regioselective and stereoselective manner, and affords synthetically challenging, but valuable linear cis-allylsilanes with excellent stereoselectivity (generally cis to trans ratios: >98:2). This cobalt-catalyzed (Z)-selective allene hydrosilylation provides a general approach to access molecules containing stereodefined (Z)-alkene units.

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Rhodium(II)-Catalyzed Stereoselective Synthesis of Allylsilanes

Cited by 16 publications

References 29 publications

Recent progress in the catalytic carbene insertion reactions into the silicon–hydrogen bond

Recent progress in the catalytic carbene insertion reactions into the silicon–hydrogen bond

Enantioselective dirhodium(II)-catalyzed cyclopropanations with trimethylsilylethyl and trichloroethyl aryldiazoacetates

Access to stereodefined (Z)-allylsilanes and (Z)-allylic alcohols via cobalt-catalyzed regioselective hydrosilylation of allenes

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