Categories: C-C Bond Formation > Carbocyclic compounds > Cyclic ketones
Synthesis of cyclohexanones
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Recent Literature
tert-Dodecanthiol-catalyzed generation of acyl radicals and their
intramolecular addition to double bonds gave 2-substituted five- and
six-membered cyclic ketones in good yields.
K. Yoshikai, T. Hayama, K. Nishimura, K.-I. Yamada, K. Tomioka, J. Org. Chem.,
2005, 70, 681-683.
Substoichiometric amounts of a Gd(OTf)3 mediate the addition of
tertiary carbon radicals generated from N-(acyloxy)phthalimide esters to
cyclic α,β-unsaturated ketones and lactones. The reaction is accomplished by
irradiation with visible light in the presence of Hantzsch ester without the use
of a photosensitizer.
S. P. Pitre, T. K. Allred, L. E. Overman, Org. Lett., 2021, 23,
1103-1106.
A cationic cyclization enables the synthesis of cyclohexanones from alkynol
or enyne derivatives with a terminal triple bond. Crucial for the success of the reaction are the
use of tetrafluoroboric acid as a promoter of the cationic cyclization, and the
selection of 1,1,1,3,3,3-hexafluoropropan-2-ol as solvent. This strategy can be extended to the biomimetic cationic cyclization of several
terpene-derived polyenynes.
P. Alsonso, R. Fonteneda, P. Pardo, F. J. Fañanás, F. Rodríguez, Org. Lett.,
2018, 20, 1659-1662.
A chiral Al(III)-N,N'-dioxide complex catalyzes an acyloin rearrangement of cyclic α-ketols to provide an array of
optically active 2-acyl-2-hydroxy cyclohexanones in good yields with
high enantioselectivities. Asymmetric isomerizations of acyclic α-hydroxy
aldehydes and α-iminols were achieved as well under modified conditions.
L. Dai, X. Li, Z. Zeng, S. Dong, Y. Zhou, X. Liu, X. Feng,
Org. Lett., 2020, 22, 5041-5045.
Enol esters can be epoxidized with high enantioselectivities using a
fructose-derived chiral ketone as catalyst and Oxone as oxidant. A subsequent
acid-catalyzed rearrangement can proceed through two distinct pathways, one with
retention of configuration and the other with inversion. Whereas a strong acid
favors retention of configuration, a weak acid favors inversion of
configuration.
Y. Zhu, L. Shu, Y. Tu, Y. Shi, J. Org. Chem., 2001,
66, 1818-1826.
Under blue-light irradiation with
1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene as photocatalyst, silyl enol
ethers reacted with alkenes in the presence of a small amount of water to afford
α-alkylated products in very good yields. A thiol cocatalyst was found to expand
the substrate scope of the reaction.
T. Hirata, Y. Ogasawara, Y. Yamashita, S. Kobayashi, Org. Lett., 2021, 23,
5693-5697.
Development of (Trimethylsilyl)ethyl Ester Protected Enolates and
Applications in Palladium-Catalyzed Enantioselective Allylic Alkylation:
Intermolecular Cross-Coupling of Functionalized Electrophiles
C. M. Reeves, D. C. Behenna, B. M. Stoltz, Org. Lett., 2014,
16, 2314-2317.
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.
The reaction of β-keto esters with CF3CO2ZnCH2I
provided the corresponding chain-extended products in moderate to good
yields. α-Substituted acyclic β-keto esters reacted less efficiently than
cyclic β-keto esters or simple β-keto esters.
S. Xue, Y.-K. Liu, L.-Z. Li, Q.-X. Guo, J. Org. Chem., 2005,
70, 8245-8247.
Ligand-free cationic Pd(II) catalyst is a highly active catalytic system for
conjugate additions of boroxines to sterically hindered γ-substituted
cyclohexenones in the presence of NaNO3 as an additive. More
challenging γγ- and βγ-substrates also react well to produce products with
quaternary centers in a highly diastereoselective fashion.
J. A. Jordan-Hore, J. N. Sanderson, A.-L. Lee, Org. Lett., 2012,
14, 2508-2511.
Pyrrolidinine-thioxotetrahydropyrimidinone derivatives were tested for their
catalytic properties in various asymmetric organic transformations. These
catalysts could efficiently catalyze the reactions in brine, without the use of
organic solvent, and by employing an almost stoichiometric amount of reagents.
Thus, the products were isolated by simple extractions in excellent yields,
diastereoselectivities, and enantioselectivities.
N. Kaplaneris, G. Koutoulogenis, M. Raftopoulou, C. G. Kokotos, J. Org. Chem.,
2015,
80, 5464-5473.
A fluorous (S)-pyrrolidine sulfonamide organocatalyst promotes highly
enantio- and diastereoselective Michael addition reactions of ketones and
aldehydes with nitroolefins in water. The organocatalyst is conveniently
recovered from the reaction mixtures by fluorous solid-phase extraction and
can be reused.
L. Zu, J. Wang, H. Li, W. Wang, Org. Lett.,
2006, 8, 3077-3079.
Two new atropisomeric electron-poor chiral diphosphine ligand analogues of
SYNPHOS were prepared, that allow a highly performant Rh-catalyzed asymmetric
1,4-addition of arylboronic acids to α,β-unsaturated carbonyl compounds at room
temperature.
F. Berhal, O. Esseiva, C.-H. Martin, H. Tone, J.-P. Genet, T. Ayad, V.
Ratovelomanana-Vidal, Org. Lett., 2011,
13, 2806-2809.
Cyclohexane-1,3-dione derivatives synthesis from unreactive acetone has been
accomplished through a consecutive Michael-Claisen process. Furthermore, the
scope of different carbonyl compounds was investigated and resulted with similar
consecutive Michael-Claisen process for CDD synthesis. The reaction exhibited
remarkable regioselectivity in Michael addition followed by Claisen cyclization.
D. Sharma, Bandna, A. K. Shil, B. Singh, P. Das, Synlett, 2012, 23,
1199-1204.
An AlCl3·MeNO2-mediated Dieckmann cyclization reaction of
general synthetic utility enables direct access to complex 2-alkyl-1,3-dione
building blocks from readily available dicarboxylic acid and acid chloride
substrates. This method enables direct access to the chiloglottone plant
pheromones from commercially available starting materials in a single synthetic
transformation.
A. M. Armaly, S. Bar, C. S. Schindler, Org. Lett.,
2017, 19, 3962-3965.
The use of acid chlorides as formal dianion linchpin reagents enables access
to cyclic 2-alkyl- and 2-acyl-1,3-alkanediones from dicarboxylic acids.
Mechanistic experiments confirm the role of acid chlorides as carbon dianion
linchpin reagents and have led to a revised reaction mechanism for the
aluminum(III)-mediated Dieckmann cyclization of dicarboxylic acids with acid
chlorides.
A. M. Armaly, S. Bar, C. S. Schindler, Org. Lett.,
2017, 19, 3958-3961.
A simple chiral primary amine catalyses a highly efficient reaction for the
synthesis of both Wieland-Miescher ketone and Hajos-Parrish ketone as well as
their analogues in high enantioselectivity and excellent yields. This procedure
represents one of the most efficient methods for the synthesis of these
versatile chiral building blocks even in gram scale with 1 mol% catalyst loading.
P. Zhou, L. Zhang, S. Luo, J.-P. Cheng, J. Org. Chem., 2012,
77, 2526-2530.