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Rh(I)-catalyzed carbonylative cyclization reactions of alkynes with 2-bromophenylboronic acids leading to indenones.
J Am Chem Soc. 2007 May 02; 129(17):5766-71.JA

Abstract

The Rh-catalyzed reaction of alkynes with 2-bromophenylboronic acids involves carbonylative cyclization to give indenones. The key steps in the reaction involve the addition of an arylrhodium(I) species to an alkyne and the oxidative addition of C-Br bonds on the adjacent phenyl ring to give vinylrhodium(I) species II. The regioselectivity depends on both the electronic and the steric nature of the substituents on the alkynes. A bulky group and an electron-withdrawing group favor the -position of indenones. In the case of silyl- or ester-substituted alkynes, the regioselectivity is extremely high. The selectivity increases in the order SiMe3 > COOR >> aryl >> alkyl. The reaction of norbornene with 2-bromophenylboronic acids under 1 atm of CO gives the corresponding indanone derivative. The reaction of alkynes with 2-bromophenylboronic acids under nitrogen gives naphthalene derivatives, in which two molecules of alkynes are incorporated. A vinylrhodium complex similar to II can also be generated by a different route by employing 2-bromophenyl(trimethylsilyl)acetylene and arylboronic acids in the presence of Rh(I) complex as the catalyst, resulting in the formation of indenones. The reaction of 1-(2-bromophenyl)-hept-2-yn-1-one with PhB(OH)2 in the presence of Rh(I) complex also resulted in carbonylative cyclization to give an indan-1,3-dione derivative.

Authors+Show Affiliations

Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan.No affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

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

Language

eng

PubMed ID

17417848

Citation

Harada, Yasuyuki, et al. "Rh(I)-catalyzed Carbonylative Cyclization Reactions of Alkynes With 2-bromophenylboronic Acids Leading to Indenones." Journal of the American Chemical Society, vol. 129, no. 17, 2007, pp. 5766-71.
Harada Y, Nakanishi J, Fujihara H, et al. Rh(I)-catalyzed carbonylative cyclization reactions of alkynes with 2-bromophenylboronic acids leading to indenones. J Am Chem Soc. 2007;129(17):5766-71.
Harada, Y., Nakanishi, J., Fujihara, H., Tobisu, M., Fukumoto, Y., & Chatani, N. (2007). Rh(I)-catalyzed carbonylative cyclization reactions of alkynes with 2-bromophenylboronic acids leading to indenones. Journal of the American Chemical Society, 129(17), 5766-71.
Harada Y, et al. Rh(I)-catalyzed Carbonylative Cyclization Reactions of Alkynes With 2-bromophenylboronic Acids Leading to Indenones. J Am Chem Soc. 2007 May 2;129(17):5766-71. PubMed PMID: 17417848.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Rh(I)-catalyzed carbonylative cyclization reactions of alkynes with 2-bromophenylboronic acids leading to indenones. AU - Harada,Yasuyuki, AU - Nakanishi,Jun, AU - Fujihara,Hirokazu, AU - Tobisu,Mamoru, AU - Fukumoto,Yoshiya, AU - Chatani,Naoto, Y1 - 2007/04/07/ PY - 2007/4/10/pubmed PY - 2007/7/26/medline PY - 2007/4/10/entrez SP - 5766 EP - 71 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 129 IS - 17 N2 - The Rh-catalyzed reaction of alkynes with 2-bromophenylboronic acids involves carbonylative cyclization to give indenones. The key steps in the reaction involve the addition of an arylrhodium(I) species to an alkyne and the oxidative addition of C-Br bonds on the adjacent phenyl ring to give vinylrhodium(I) species II. The regioselectivity depends on both the electronic and the steric nature of the substituents on the alkynes. A bulky group and an electron-withdrawing group favor the -position of indenones. In the case of silyl- or ester-substituted alkynes, the regioselectivity is extremely high. The selectivity increases in the order SiMe3 > COOR >> aryl >> alkyl. The reaction of norbornene with 2-bromophenylboronic acids under 1 atm of CO gives the corresponding indanone derivative. The reaction of alkynes with 2-bromophenylboronic acids under nitrogen gives naphthalene derivatives, in which two molecules of alkynes are incorporated. A vinylrhodium complex similar to II can also be generated by a different route by employing 2-bromophenyl(trimethylsilyl)acetylene and arylboronic acids in the presence of Rh(I) complex as the catalyst, resulting in the formation of indenones. The reaction of 1-(2-bromophenyl)-hept-2-yn-1-one with PhB(OH)2 in the presence of Rh(I) complex also resulted in carbonylative cyclization to give an indan-1,3-dione derivative. SN - 0002-7863 UR - https://www.unboundmedicine.com/medline/citation/17417848/Rh_I__catalyzed_carbonylative_cyclization_reactions_of_alkynes_with_2_bromophenylboronic_acids_leading_to_indenones_ L2 - https://doi.org/10.1021/ja070107n DB - PRIME DP - Unbound Medicine ER -