Molecular rearrangements of organosilicon compounds

Brook, A. G.

doi:10.1021/ar50075a003

Cited by 717 publications

(357 citation statements)

References 223 publications

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“…[34,35] We conjectured that the mandatory use of triphenylsilanes likely reflects the need to lower the energy of the C-Si antibondingo rbital as ap reludef or successfula ttack of the adjacent alkoxide onto the silicon atom that triggers the critical Brook rearrangement; [36,37] this step is arguably challenging as it passes throughaf our-membered intermediate O.U nder the premise that orbitale nergy lowering is the key to success, however,s ilanes of type B carrying electronegative heteroatoms at silicon should also qualify as substrates. [38] Alkoxysilanes B (X = OR), which are easy to make via the ruthenium catalyzed trans-hydrosilylation referred to above, [12,13] fall into this category and were therefore deemed ap otentially very attractive and versatile class of startingm aterials.…”

Section: The Key Organocopper Intermediate Eh Oweveri Sn Ot the Onlmentioning

confidence: 99%

Two Enabling Strategies for the Stereoselective Conversion of Internal Alkynes into Trisubstituted Alkenes

Huwyler

Radkowski

Rummelt

et al. 2017

Chemistry A European J

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An expedient methodf or the C-methylation of alkenylstannanes with formation of trisubstituted alkenes is described, which relies on the use of MeI in combination with coppert hiophene-2-carboxylate (CuTC) as promotor and tetra-n-butylammonium diphenylphosphinate as an effective tin scavenger;i ns ome cases, it proved beneficial to further supplement the mixture with catalytic amounts of Pd(PPh 3 ) 4 .U nder these conditions, the reactioni sr obust, high yielding, and compatible with many functional groups that might not subsist under more traditional conditions used to C-alkylate organotin derivatives. Aq ualitative analysis of the reaction profile suggested that the in situ formation of ar eactive organocopper intermediate and its interception by MeI is only barely faster than O-methylation of the phosphinate additive by the same alkylating agent.T o guarantee high yields and prevent net protodestannation from occurring, the reaction protocolh ad to be optimized such that these competing processes are properly decoupled. The new methodi sp articularly well suited for the stereoselectivep reparation of the (E)-2-methylbut-2-en-1-ol motif that is presenti nn umerous natural products. Alternatively,t his particular target structure canb ea ccesseds tarting from a-hydroxy alkenylsiloxane precursors, which get Cmethylated upon exposure to CuI/LiOtBu and MeI by what is thought to be aB rookr earrangement/ alkylations equence. The required substrates are best prepared by ruthenium-catalyzed trans-hydrosilylation or trans-hydrostannation of propargyl alcohols.

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Section: The Key Organocopper Intermediate Eh Oweveri Sn Ot the Onlmentioning

confidence: 99%

Two Enabling Strategies for the Stereoselective Conversion of Internal Alkynes into Trisubstituted Alkenes

Huwyler

Radkowski

Rummelt

et al. 2017

Chemistry A European J

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“…This indicated that the ion-rich culture medium at pH 8 catalyzed the conversion of hydroxymethylsilanetriol to silicic acid. It should be noted that this is potentially a Brook rearrangement [34]. The utilization of hydroxymethylsilanetriol as a substrate for growth of C. fusiformis should not be taken as an indication that it is incorporated into the siliceous structure.…”

Section: Diatom Studiesmentioning

confidence: 99%

Hydroxymethylsilanetriol – A Simple Analog of Silicic Acid

Arkles

King

Pannell

2013

Silicon

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Hydroxymethyltriethoxysilane and hydroxymethyltrimethoxysilane, precursors by hydrolysis to a simple analog of silicic acid, hydroxymethylsilanetriol, were prepared. Hydroxymethyltrialkoxysilanes undergo condensation to form silmethyleneoxide oligomers and dimeric 2,2,5,5-tetraalkoxy-2,5-disila-1,4-dioxanes. Hydroxymethylsilanetriol undergoes condensation reactions similar to silicic acid and readily forms organosilicate structures by sol-gel processing techniques which may be converted at relatively low temperatures to silicon dioxide. Hydroxmethylsilanetriol derived gels were subject to less stresscracking during drying than conventional tetraethoxysilane derived gels, suggesting that Si-O-C bond equilibration during drying provides a mechanism for stress-relief. In screening experiments, hydroxymethylsilanetriol appears to be a competitive inhibitor of the growth of the diatom C. fusiformis, a silicate dependent species, which produces silicate structures.

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“…In the next step, dimethyl ester 19 was synthesized using sodium dimethyl malonate by adopting Malleron procedure 12 . Ester 19 was further heated in DMSO with sodium chloride to furnish 20 13 . To introduce phenylsulphonyl in 20, simple and high yielding functional group inter conversion was adopted to achieve the synthesis of component B 3.…”

Section: Methodsmentioning

confidence: 99%

Advances in Total Synthesis of Alternaric Acid: An Anti-Fungal and Phytotoxic Natural Product

Ahmad

Yousaf

Zahoor

et al. 2017

J. Chil. Chem. Soc.

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ABSTRACT:Alternaric acid is characterized as 1,4-diene, possessing (E)-1,2-disubstituted alkene known for nanomolar phytotoxic and antifungal activities. This article highlights the major synthetic approaches attempted towards the total synthesis of alternaric acid reported by three groups (Ichihara & coworkers, Trost & coworkers and Johnson and Slade) which involved novel pathways for the rapid construction of this functionalized natural molecule.

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Molecular rearrangements of organosilicon compounds

Cited by 717 publications

References 223 publications

Two Enabling Strategies for the Stereoselective Conversion of Internal Alkynes into Trisubstituted Alkenes

Two Enabling Strategies for the Stereoselective Conversion of Internal Alkynes into Trisubstituted Alkenes

Hydroxymethylsilanetriol – A Simple Analog of Silicic Acid

Advances in Total Synthesis of Alternaric Acid: An Anti-Fungal and Phytotoxic Natural Product

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