Abstract
Herein described is the chelation-assisted C-C bond activation of unstrained ketones under the co-catalyst system of Rh(PPh3)3Cl and 2-amino-3-picoline (1). This reaction is based on the strategy we recently developed in hydroacylation with aldehydes in which 2-aminopyridine derivatives function as chelation-assistant tools. Unstrained ketones having a β-hydrogen gave rise to alkyl-exchanged ketones via this C-C bond activation under an excess of external olefins. In the absence of external olefins, cycloheptanone underwent a ring contraction to generate five- and six-membered cyclic ketones. Instead of unstrained ketones, sec-alcohols were also employed as a substrate for this C-C bond activation via hydrogen transfer. The reaction of allylamine derivatives under [Rh(C8H14)2Cl]2 and PCy3 afforded symmetric dialkyl ketones via a series of reaction such as olefin isomerization, C-H bond activation, and C-C bond activation. The key intermediate, the imine derived from 1 was generated from a primary amine through dehydrogenation followed by transimination. Consequently, the Rh(I)-catalyzed C-C bond activation of unstrained ketones and their equivalents was demonstrated by utilizing a chelation-assistance strategy.
| Original language | English |
|---|---|
| Pages (from-to) | 145-156 |
| Number of pages | 12 |
| Journal | Journal of Molecular Catalysis A: Chemical |
| Volume | 189 |
| Issue number | 1 |
| DOIs | |
| Publication status | Published - 2002 Oct 16 |
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All Science Journal Classification (ASJC) codes
- Catalysis
- Process Chemistry and Technology
- Physical and Theoretical Chemistry
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Chelation-assisted carbon-carbon bond activation by Rh(I) catalysts. / Jun, Chul Ho; Moon, Choong Woon; Lee, Hyuk; Lee, Dae Yon.
In: Journal of Molecular Catalysis A: Chemical, Vol. 189, No. 1, 16.10.2002, p. 145-156.Research output: Contribution to journal › Article
TY - JOUR
T1 - Chelation-assisted carbon-carbon bond activation by Rh(I) catalysts
AU - Jun, Chul Ho
AU - Moon, Choong Woon
AU - Lee, Hyuk
AU - Lee, Dae Yon
PY - 2002/10/16
Y1 - 2002/10/16
N2 - Herein described is the chelation-assisted C-C bond activation of unstrained ketones under the co-catalyst system of Rh(PPh3)3Cl and 2-amino-3-picoline (1). This reaction is based on the strategy we recently developed in hydroacylation with aldehydes in which 2-aminopyridine derivatives function as chelation-assistant tools. Unstrained ketones having a β-hydrogen gave rise to alkyl-exchanged ketones via this C-C bond activation under an excess of external olefins. In the absence of external olefins, cycloheptanone underwent a ring contraction to generate five- and six-membered cyclic ketones. Instead of unstrained ketones, sec-alcohols were also employed as a substrate for this C-C bond activation via hydrogen transfer. The reaction of allylamine derivatives under [Rh(C8H14)2Cl]2 and PCy3 afforded symmetric dialkyl ketones via a series of reaction such as olefin isomerization, C-H bond activation, and C-C bond activation. The key intermediate, the imine derived from 1 was generated from a primary amine through dehydrogenation followed by transimination. Consequently, the Rh(I)-catalyzed C-C bond activation of unstrained ketones and their equivalents was demonstrated by utilizing a chelation-assistance strategy.
AB - Herein described is the chelation-assisted C-C bond activation of unstrained ketones under the co-catalyst system of Rh(PPh3)3Cl and 2-amino-3-picoline (1). This reaction is based on the strategy we recently developed in hydroacylation with aldehydes in which 2-aminopyridine derivatives function as chelation-assistant tools. Unstrained ketones having a β-hydrogen gave rise to alkyl-exchanged ketones via this C-C bond activation under an excess of external olefins. In the absence of external olefins, cycloheptanone underwent a ring contraction to generate five- and six-membered cyclic ketones. Instead of unstrained ketones, sec-alcohols were also employed as a substrate for this C-C bond activation via hydrogen transfer. The reaction of allylamine derivatives under [Rh(C8H14)2Cl]2 and PCy3 afforded symmetric dialkyl ketones via a series of reaction such as olefin isomerization, C-H bond activation, and C-C bond activation. The key intermediate, the imine derived from 1 was generated from a primary amine through dehydrogenation followed by transimination. Consequently, the Rh(I)-catalyzed C-C bond activation of unstrained ketones and their equivalents was demonstrated by utilizing a chelation-assistance strategy.
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U2 - 10.1016/S1381-1169(02)00202-9
DO - 10.1016/S1381-1169(02)00202-9
M3 - Article
AN - SCOPUS:0037120662
VL - 189
SP - 145
EP - 156
JO - Journal of Molecular Catalysis A: Chemical
JF - Journal of Molecular Catalysis A: Chemical
SN - 1381-1169
IS - 1
ER -