[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 stable at -78 °C and undergoes diastereoselective syn-addition at the γ-position with aldehydes and ketones to give monobenzyl-substituted 1,2-diols.
Key Laboratory of Drug-Targeting of Education Ministry and Department of Medicinal Chemistry, West China School of Pharmacy, ‡State Key Laboratory of Biotherapy, West China Hospital, Sichuan University , Chengdu 610041, P. R. China.
Xinglong
X
Lin
Xincui
X
Ye
Xianwei
X
Sun
Yuebao
Y
Zhang
Lu
L
Gao
Zhenlei
Z
Song
D000447:Aldehydes / Q000737:chemistry*; D000838:Anions / Q000737:chemistry; D004987:Ethers / Q000737:chemistry; D007659:Ketones / Q000737:chemistry*; D008094:Lithium / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D011522:Protons; D012821:Silanes / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
D000447:Aldehydes; D000838:Anions; D004987:Ethers; D007659:Ketones; D009942:Organometallic Compounds; D011522:Protons; D012821:Silanes; D008094:Lithium