Bistrimethylsilylpropargylic ether: a versatile ambident synthon to access substituted allenyne ethers and alpha-substituted bispropargylic alcohols.
The reactivity of 1,5-bis(trimethylsilyl)propargylic ethers 3 toward bases and electrophiles was investigated. Bispropargylic ethers 4, substituted allenyne ethers 6-8, and alpha-substituted bispropargylic ethers 9 were prepared in good yields, respectively, by protodesilylation, isomerization, or metalation/alkylation of bispropargylic protected alcohol 3. The ambident behavior of metalated synthon 3 was discussed and rationalized. Removal of the protecting groups of 9 easily afforded useful alpha-substituted bispropargylic alcohol.
Brossat
Maude
M
CEA-Saclay, iBiTec-S, Service de Chimie Bioorganique et de Marquage, Bât 547, F-91191 Gif sur Yvette cedex, France.
Heck
Marie-Pierre
MP
Mioskowski
Charles
C
D000480:Alkynes / Q000737:chemistry*; D004987:Ethers / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D020005:Propanols / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization; D013056:Spectrophotometry, Ultraviolet
D000480:Alkynes; D004987:Ethers; D020005:Propanols; C028255:propargyl alcohol