[1,5]-Anion Relay via Intramolecular Proton Transfer To Generate 3,3-Bis(silyl) Allyloxy Lithium: A Useful Scaffold for Syn-Addition to Aldehydes and Ketones

[1,5]-Anion Relay via Intramolecular Proton Transfer To Generate 3,3-Bis(silyl) Allyloxy Lithium: A Useful Scaffold for Syn-Addition to Aldehydes and Ketones

A [1,5]-anion relay has been achieved in 3,3-bis(silyl) benzyl enol ether. Deprotonation at the sterically more accessible benzyl position triggers an intramolecular proton transfer to generate the thermodynamically more stable 3,3-bis(silyl) allyloxy lithium. This endo-oriented allyl anion is stabl...

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Veröffentlicht in:Organic letters 2014-02, Vol.16 (4), p.1084-1087
Hauptverfasser: Lin, Xinglong, Ye, Xincui, Sun, Xianwei, Zhang, Yuebao, Gao, Lu, Song, Zhenlei
Format: Artikel
Sprache:eng
Schlagworte:
Aldehydes - chemistry
Anions - chemistry
Ethers - chemistry
Ketones - chemistry
Lithium - chemistry
Molecular Structure
Organometallic Compounds - chemical synthesis
Organometallic Compounds - chemistry
Protons
Silanes - chemical synthesis
Silanes - chemistry
Stereoisomerism
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Zusammenfassung:A [1,5]-anion relay has been achieved in 3,3-bis(silyl) benzyl enol ether. Deprotonation at the sterically more accessible benzyl position triggers an intramolecular proton transfer to generate the thermodynamically more stable 3,3-bis(silyl) allyloxy lithium. This endo-oriented allyl anion is stable at −78 °C and undergoes diastereoselective syn-addition at the γ-position with aldehydes and ketones to give monobenzyl-substituted 1,2-diols.
ISSN:1523-7060
1523-7052
DOI:10.1021/ol4036402