Abstract
Efficient and selective substitution of cyclic and acyclic vinyl ethers with photo-generated difluoromethyl radicals bearing ester and phosphonate groups, in the presence of 2,4,6-trimethylpyridine and diphenyl diselenide was successfully carried out to provide the corresponding regioselective unsaturated difluoromethylene adducts selectively. The reaction involves phenylselenyl transfer at an early stage followed by elimination of phenylselenol from the adducts once formed to provide the unsaturated difluoromethylene adducts selectively. This novel photochemical method was successfully extended to aromatic and heteroaromatic substitutions to provide the corresponding α-aryl-α,α-difluoroacetates and α-aryl-α,α- difluoromethylphosphonates in good to moderate yields.
| Original language | English |
|---|---|
| Pages (from-to) | 3761-3769 |
| Number of pages | 9 |
| Journal | Tetrahedron |
| Volume | 62 |
| Issue number | 15 |
| DOIs | |
| Publication status | Published - 2006 Apr 10 |
| Externally published | Yes |
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Keywords
- C-CF bond formation
- Difluoromethyl radicals
- Group transfer
- Photoreaction
- Selenide
ASJC Scopus subject areas
- Biochemistry
- Organic Chemistry
- Drug Discovery
Cite this
Photochemical substitution of olefins and aromatic compounds with difluoromethyl radicals bearing ester and phosphonate groups. / Murakami, Satoru; Ishii, Hideki; Tajima, Toshiki; Fuchigami, Toshio.
In: Tetrahedron, Vol. 62, No. 15, 10.04.2006, p. 3761-3769.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Photochemical substitution of olefins and aromatic compounds with difluoromethyl radicals bearing ester and phosphonate groups
AU - Murakami, Satoru
AU - Ishii, Hideki
AU - Tajima, Toshiki
AU - Fuchigami, Toshio
PY - 2006/4/10
Y1 - 2006/4/10
N2 - Efficient and selective substitution of cyclic and acyclic vinyl ethers with photo-generated difluoromethyl radicals bearing ester and phosphonate groups, in the presence of 2,4,6-trimethylpyridine and diphenyl diselenide was successfully carried out to provide the corresponding regioselective unsaturated difluoromethylene adducts selectively. The reaction involves phenylselenyl transfer at an early stage followed by elimination of phenylselenol from the adducts once formed to provide the unsaturated difluoromethylene adducts selectively. This novel photochemical method was successfully extended to aromatic and heteroaromatic substitutions to provide the corresponding α-aryl-α,α-difluoroacetates and α-aryl-α,α- difluoromethylphosphonates in good to moderate yields.
AB - Efficient and selective substitution of cyclic and acyclic vinyl ethers with photo-generated difluoromethyl radicals bearing ester and phosphonate groups, in the presence of 2,4,6-trimethylpyridine and diphenyl diselenide was successfully carried out to provide the corresponding regioselective unsaturated difluoromethylene adducts selectively. The reaction involves phenylselenyl transfer at an early stage followed by elimination of phenylselenol from the adducts once formed to provide the unsaturated difluoromethylene adducts selectively. This novel photochemical method was successfully extended to aromatic and heteroaromatic substitutions to provide the corresponding α-aryl-α,α-difluoroacetates and α-aryl-α,α- difluoromethylphosphonates in good to moderate yields.
KW - C-CF bond formation
KW - Difluoromethyl radicals
KW - Group transfer
KW - Photoreaction
KW - Selenide
UR - http://www.scopus.com/inward/record.url?scp=33645008390&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=33645008390&partnerID=8YFLogxK
U2 - 10.1016/j.tet.2005.12.057
DO - 10.1016/j.tet.2005.12.057
M3 - Article
AN - SCOPUS:33645008390
VL - 62
SP - 3761
EP - 3769
JO - Tetrahedron
JF - Tetrahedron
SN - 0040-4020
IS - 15
ER -