Abstract
A conceptually distinct, modern strategy for Baeyer-Villiger oxidation (BVO) was developed. Our novel method involves initial hydration of water to carbonyl compounds, followed by ligand exchange of hypervalent aryl-λ3-bromane on bromane(III) with the resulting hydrate, yielding a new type of activated Criegee intermediate. The intermediate undergoes BV rearrangement and produces an ester via facile reductive elimination of an aryl-λ3-bromanyl group, because of the hypernucleofugality. The novel strategy makes it possible to induce selectively the BV rearrangement of straight chain primary aliphatic as well as aromatic aldehydes, which is missing in the classical BVO: for instance, octanal and benzaldehyde afforded rearranged formate esters with high selectivity (>95%) under our conditions, while the attempted classical BVO produced only carboxylic acids. This firmly establishes the powerful nature of new methodology for BVO.
| Original language | English |
|---|---|
| Pages (from-to) | 9236-9239 |
| Number of pages | 4 |
| Journal | Journal of the American Chemical Society |
| Volume | 132 |
| Issue number | 27 |
| DOIs | |
| Publication status | Published - 14 Jul 2010 |
| Externally published | Yes |
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ASJC Scopus subject areas
- Catalysis
- Chemistry(all)
- Biochemistry
- Colloid and Surface Chemistry
Cite this
Hypervalent λ3-bromane strategy for Baeyer-Villiger oxidation : Selective transformation of primary aliphatic and aromatic aldehydes to formates, which is missing in the classical Baeyer-Villiger oxidation. / Ochiai, Masahito; Yoshimura, Akira; Miyamoto, Kazunori; Hayashi, Satoko; Nakanishi, Waro.
In: Journal of the American Chemical Society, Vol. 132, No. 27, 14.07.2010, p. 9236-9239.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Hypervalent λ3-bromane strategy for Baeyer-Villiger oxidation
T2 - Selective transformation of primary aliphatic and aromatic aldehydes to formates, which is missing in the classical Baeyer-Villiger oxidation
AU - Ochiai, Masahito
AU - Yoshimura, Akira
AU - Miyamoto, Kazunori
AU - Hayashi, Satoko
AU - Nakanishi, Waro
PY - 2010/7/14
Y1 - 2010/7/14
N2 - A conceptually distinct, modern strategy for Baeyer-Villiger oxidation (BVO) was developed. Our novel method involves initial hydration of water to carbonyl compounds, followed by ligand exchange of hypervalent aryl-λ3-bromane on bromane(III) with the resulting hydrate, yielding a new type of activated Criegee intermediate. The intermediate undergoes BV rearrangement and produces an ester via facile reductive elimination of an aryl-λ3-bromanyl group, because of the hypernucleofugality. The novel strategy makes it possible to induce selectively the BV rearrangement of straight chain primary aliphatic as well as aromatic aldehydes, which is missing in the classical BVO: for instance, octanal and benzaldehyde afforded rearranged formate esters with high selectivity (>95%) under our conditions, while the attempted classical BVO produced only carboxylic acids. This firmly establishes the powerful nature of new methodology for BVO.
AB - A conceptually distinct, modern strategy for Baeyer-Villiger oxidation (BVO) was developed. Our novel method involves initial hydration of water to carbonyl compounds, followed by ligand exchange of hypervalent aryl-λ3-bromane on bromane(III) with the resulting hydrate, yielding a new type of activated Criegee intermediate. The intermediate undergoes BV rearrangement and produces an ester via facile reductive elimination of an aryl-λ3-bromanyl group, because of the hypernucleofugality. The novel strategy makes it possible to induce selectively the BV rearrangement of straight chain primary aliphatic as well as aromatic aldehydes, which is missing in the classical BVO: for instance, octanal and benzaldehyde afforded rearranged formate esters with high selectivity (>95%) under our conditions, while the attempted classical BVO produced only carboxylic acids. This firmly establishes the powerful nature of new methodology for BVO.
UR - http://www.scopus.com/inward/record.url?scp=77955807307&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=77955807307&partnerID=8YFLogxK
U2 - 10.1021/ja104330g
DO - 10.1021/ja104330g
M3 - Article
C2 - 20568756
AN - SCOPUS:77955807307
VL - 132
SP - 9236
EP - 9239
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 27
ER -