Categories: C-C Bond Formation > Oxygen-, Nitrogen-containing molecules

Substitution of active methylenes

Related:

Name Reactions

Recent Literature

F. Stauffer, R. Neier, Org. Lett., 2000, 2, 3535-3537.

The coupling of aryl iodides and diethyl malonate in the presence of Cs₂CO₃ and catalytic amounts of CuI and 2-phenylphenol gave α-aryl malonates in good to excellent yields. This mild method tolerates various functional groups.
E. J. Hennessy, S. L. Buchwald, Org. Lett., 2002, 4, 269-272.

2-aryl-1,3-dicarbonyl compounds are produced in good yields by a CuI/L-proline-catalyzed arylation of activated methylene compounds with aryl iodides and aryl bromides in DMSO at 40-50°C in the presence of Cs₂CO₃.
X. Xie, G. Cai, D. Ma, Org. Lett., 2005, 7, 4693-4695.

Simple dialkyl malonate esters exhibit limited scope as carbon nucleophiles in the Mitsunobu reaction. In contrast, bis(2,2,2-trifluoroethyl) malonates readily undergo dehydrative alkylation with primary and some secondary alcohols.
J. M. Takacs, Z. Xu, X.-T. Jiang, A. P. Leonov, G. C. Theriot, Org. Lett., 2002, 4, 3843-3845.

AuCl₃/AgOTf catalyzes a highly efficient intermolecular addition of 1,3-diketones to alkenes. A proposed mechanism for the reaction is based on α-C-H activation.
X. Yao, C.-J. Li, J. Am. Chem. Soc., 2004, 126, 6884-6885.

Environmentally benign additions of various 1,3-dicarbonyl compounds to alkenes and alcohols in the presence of solid acid catalysts have been described.
K. Motokura, N. Fujita, K. Mori, T. Mizugaki, K. Ebitani, K. Kaneda, Angew. Chem. Int. Ed., 2006, 45, 2605-2609.

K. Motokura, N. Fujita, K. Mori, T. Mizugaki, K. Ebitani, K. Kaneda, Angew. Chem. Int. Ed., 2006, 45, 2605-2609.

A highly enantioselective catalytic alkylation of cyanoacetates was achieved using a chiral phase-transfer catalyst to give α,α-disubstituted α-cyanoacetates which have a chiral quaternary carbon.
K. Nagata, D. Sano, T. Itoh, Synlett, 2007, 547-550.

Alkylation of the aza-enolate of valerolactim methyl ether with electrophiles affords α-alkyl lactims. Subsequent mild, acidic hydrolysation gives the corresponding α-alkyl-δ-amino esters hydrochloride salts. Neutralisation of these salts with base results in smooth intramolecular cyclisation to afford α-alkyl lactams in excellent yield.
P. J. M. Taylor, S. D. Bull, P. C. Andrews, Synlett, 2006, 1347-1350.

In the presence of PdCl₂(MeCN)₂, CuCl₂, and PEG-400, various alkenyl β-keto esters and amides underwent a selective cyclization to give six-membered carbocycles in good to excellent yields. The PdCl₂(MeCN)₂/CuCl₂/PEG-400 system could be recycled and reused five times without any loss of catalytic activity.
J.-H. Li, Q.-M. Zhu, Y. Liang, D. Yang, J. Org. Chem., 2005, 70, 5347-5349.

Achiral and chiral phosphorodiamidic acids were developed as efficient Brønsted acid catalysts for the direct Mannich reaction of N-acyl imines with 1,3-dicarbonyl compounds.
M. Terada, K. Sorimachi, D. Uraguchi, Synlett, 2006, 133-134.

Efficient carbon-carbon bond formation of N-carbobenzyloxy amines with 1,3-dicarbonyl compounds at the α-position of nitrogen was established by a one-pot oxidative Mannich reaction using N-tert-butylbenzenesulfinimidoyl chloride as an oxidant.
J-I. Matsuo, Y. Tanaki, H. Ishibashi, Org. Lett., 2006, 8, 4371-4374.