Abstract
The "halocarbocyclization reaction", which involves an intramolecular attack of a carbon nucleophile on a double bond activated by an electrophilic halogenating reagent, has so far been uncommon. We report here that the "iodocarbocyclization reaction" of alkenyl or alkynylmalonate derivatives proceeded in good yields in the presence of Ti(OR)4 and I2 to give cyclized products in a highly regio-and stereospecific manner. The diastereoselective iodocarbocyclization with 4-pentenylmalonate derivatives having a chiral center at the allylic or homoallylic position and allylmalonate having a chiral auxiliary in the ester part has also been investigated. Furthermore, the reaction of 4-pentenylmalonate using a catalytic amount of a chiral titanium alkoxide in the presence of I2 and 2,6-dimethoxypyridine proceeded with high enantioselectivity to give good yields of cyclopentane derivatives. The origin of enantioselectivity in this catalytic asymmetric reaction is also described.
| Original language | English |
|---|---|
| Pages (from-to) | 243-262 |
| Number of pages | 20 |
| Journal | Reviews on Heteroatom Chemistry |
| Volume | 15 |
| Publication status | Published - 1996 |
| Externally published | Yes |
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Keywords
- Catalytic asymmetric reaction
- Chiral ligand
- Diastereoselective reaction
- Iodine
- Iodocarbocyclization reaction
- Stereospecific reaction
- Titanium alkoxide
ASJC Scopus subject areas
- Inorganic Chemistry
Cite this
Iodocarbocyclization reaction. / Kitagawa, Osamu; Inoue, Tadashi; Taguchi, Takeo.
In: Reviews on Heteroatom Chemistry, Vol. 15, 1996, p. 243-262.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Iodocarbocyclization reaction
AU - Kitagawa, Osamu
AU - Inoue, Tadashi
AU - Taguchi, Takeo
PY - 1996
Y1 - 1996
N2 - The "halocarbocyclization reaction", which involves an intramolecular attack of a carbon nucleophile on a double bond activated by an electrophilic halogenating reagent, has so far been uncommon. We report here that the "iodocarbocyclization reaction" of alkenyl or alkynylmalonate derivatives proceeded in good yields in the presence of Ti(OR)4 and I2 to give cyclized products in a highly regio-and stereospecific manner. The diastereoselective iodocarbocyclization with 4-pentenylmalonate derivatives having a chiral center at the allylic or homoallylic position and allylmalonate having a chiral auxiliary in the ester part has also been investigated. Furthermore, the reaction of 4-pentenylmalonate using a catalytic amount of a chiral titanium alkoxide in the presence of I2 and 2,6-dimethoxypyridine proceeded with high enantioselectivity to give good yields of cyclopentane derivatives. The origin of enantioselectivity in this catalytic asymmetric reaction is also described.
AB - The "halocarbocyclization reaction", which involves an intramolecular attack of a carbon nucleophile on a double bond activated by an electrophilic halogenating reagent, has so far been uncommon. We report here that the "iodocarbocyclization reaction" of alkenyl or alkynylmalonate derivatives proceeded in good yields in the presence of Ti(OR)4 and I2 to give cyclized products in a highly regio-and stereospecific manner. The diastereoselective iodocarbocyclization with 4-pentenylmalonate derivatives having a chiral center at the allylic or homoallylic position and allylmalonate having a chiral auxiliary in the ester part has also been investigated. Furthermore, the reaction of 4-pentenylmalonate using a catalytic amount of a chiral titanium alkoxide in the presence of I2 and 2,6-dimethoxypyridine proceeded with high enantioselectivity to give good yields of cyclopentane derivatives. The origin of enantioselectivity in this catalytic asymmetric reaction is also described.
KW - Catalytic asymmetric reaction
KW - Chiral ligand
KW - Diastereoselective reaction
KW - Iodine
KW - Iodocarbocyclization reaction
KW - Stereospecific reaction
KW - Titanium alkoxide
UR - http://www.scopus.com/inward/record.url?scp=0030527155&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0030527155&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:0030527155
VL - 15
SP - 243
EP - 262
JO - Reviews on Heteroatom Chemistry
JF - Reviews on Heteroatom Chemistry
SN - 0915-6151
ER -