Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 55, Issue 3, Pages 1151-1155Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201510006
Keywords
allenes; density-functional calculations; iron; oxidation; synthetic methods
Categories
Funding
- University of Illinois at Chicago (LAS Science Award)
- NSF [CHE 0955972]
- TACOMA technology
- Zhejiang Provincial NSF [LY13B020007]
- NSFC [21372178, 21572163]
Ask authors/readers for more resources
Substituent- and oxidant-dependent transformations of allenes are described. Given the profound influence of the substituent on the reactivity of allenes, the subtle differences in allene structures are manifested in the formation of diverse products when reacted with different electrophiles/oxidants. In general, reactions of nonsilylated allenes involve an allylic cation intermediate by forming a C-O bond, at the sp-hybridized C2, with either DDQ (2,3-dichloro-5,6-dicyano-p-benzoquinone) or TBHP (tert-butyl hydroperoxide), along with FeCl(2)4H(2)O (10mol %). In contrast, silylated allenes favor the formation of propargylic cation intermediates by transferring the allenic hydride to the oxidant, thus generating 1,3-enynes (E1 product) or propargylic THBP ethers (S(N)1 product). The formation of these different putative cationic intermediates from nonsilylated and silylated allenes is strongly supported by DFT calculations.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available