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Rhodium-catalyzed nondecarbonylative addition reaction of ClCOCOOC2H5 to alkynes.
Chemistry. 2005 Jun 06; 11(12):3621-30.C

Abstract

Addition of ethoxalyl chloride (ClCOCOOEt) to terminal alkynes at 60 degrees C in the presence of a rhodium(I)-phosphine complex catalyst chosen from a wide range affords 4-chloro-2-oxo-3-alkenoates regio- and stereoselectively. Functional groups such as chloro, cyano, alkoxy, siloxy, and hydroxy are tolerated. The oxidative addition of ethoxalyl chloride to [RhCl(CO)(PR(3))(2)] proceeds readily at 60 degrees C or room temperature and gives [RhCl(2)(COCOOEt)(CO)(PR(3))(2)] (PR(3) = PPh(2)Me, PPhMe(2), PMe(3)) complexes in high yields. The structure of [RhCl(2)(COCOOEt)(CO)(PPh(2)Me)(2)] was confirmed by X-ray crystallography. Thermolysis of these ethoxalyl complexes has revealed that those ligated by more electron-donating phosphines are fairly stable against decarbonylation and reductive elimination. [RhCl(2)(COCOOEt)(CO)(PPh(2)Me)(2)] reacts with 1-octyne at 60 degrees C to form ethyl 4-chloro-2-oxo-3-decenoate. The catalysis is therefore proposed to proceed by oxidative addition of ethoxalyl chloride, insertion of an alkyne into the Cl--Rh bond of the resulting intermediate, and reductive elimination of alkenyl-COCOOEt.

Authors+Show Affiliations

Hua R
Department of Chemistry, Tsinghua University, Beijing, P. R. China.
Onozawa SY
No affiliation info available
Tanaka M
No affiliation info available

MeSH

AlkynesCatalysisCrystallography, X-RayEstersHydrocarbons, ChlorinatedModels, MolecularMolecular StructureOrganometallic CompoundsOxidation-ReductionRhodium

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

15809987

Citation

Hua, Ruimao, et al. "Rhodium-catalyzed Nondecarbonylative Addition Reaction of ClCOCOOC2H5 to Alkynes." Chemistry (Weinheim an Der Bergstrasse, Germany), vol. 11, no. 12, 2005, pp. 3621-30.
Hua R, Onozawa SY, Tanaka M. Rhodium-catalyzed nondecarbonylative addition reaction of ClCOCOOC2H5 to alkynes. Chemistry. 2005;11(12):3621-30.
Hua, R., Onozawa, S. Y., & Tanaka, M. (2005). Rhodium-catalyzed nondecarbonylative addition reaction of ClCOCOOC2H5 to alkynes. Chemistry (Weinheim an Der Bergstrasse, Germany), 11(12), 3621-30.
Hua R, Onozawa SY, Tanaka M. Rhodium-catalyzed Nondecarbonylative Addition Reaction of ClCOCOOC2H5 to Alkynes. Chemistry. 2005 Jun 6;11(12):3621-30. PubMed PMID: 15809987.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Rhodium-catalyzed nondecarbonylative addition reaction of ClCOCOOC2H5 to alkynes. AU - Hua,Ruimao, AU - Onozawa,Shun-Ya, AU - Tanaka,Masato, PY - 2005/4/6/pubmed PY - 2006/1/19/medline PY - 2005/4/6/entrez SP - 3621 EP - 30 JF - Chemistry (Weinheim an der Bergstrasse, Germany) JO - Chemistry VL - 11 IS - 12 N2 - Addition of ethoxalyl chloride (ClCOCOOEt) to terminal alkynes at 60 degrees C in the presence of a rhodium(I)-phosphine complex catalyst chosen from a wide range affords 4-chloro-2-oxo-3-alkenoates regio- and stereoselectively. Functional groups such as chloro, cyano, alkoxy, siloxy, and hydroxy are tolerated. The oxidative addition of ethoxalyl chloride to [RhCl(CO)(PR(3))(2)] proceeds readily at 60 degrees C or room temperature and gives [RhCl(2)(COCOOEt)(CO)(PR(3))(2)] (PR(3) = PPh(2)Me, PPhMe(2), PMe(3)) complexes in high yields. The structure of [RhCl(2)(COCOOEt)(CO)(PPh(2)Me)(2)] was confirmed by X-ray crystallography. Thermolysis of these ethoxalyl complexes has revealed that those ligated by more electron-donating phosphines are fairly stable against decarbonylation and reductive elimination. [RhCl(2)(COCOOEt)(CO)(PPh(2)Me)(2)] reacts with 1-octyne at 60 degrees C to form ethyl 4-chloro-2-oxo-3-decenoate. The catalysis is therefore proposed to proceed by oxidative addition of ethoxalyl chloride, insertion of an alkyne into the Cl--Rh bond of the resulting intermediate, and reductive elimination of alkenyl-COCOOEt. SN - 0947-6539 UR - https://www.unboundmedicine.com/medline/citation/15809987/Rhodium_catalyzed_nondecarbonylative_addition_reaction_of_ClCOCOOC2H5_to_alkynes_ DB - PRIME DP - Unbound Medicine ER -