Categories: Synthesis of O-Heterocycles, C-O Bond Formation >
Synthesis of lactones and related compounds
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Recent Literature
Silver(I) triflate catalyzes intramolecular additions of hydroxyl or carboxyl groups to olefins
in good to excellent yields for a range of substrates under relatively mild conditions. This
reaction is one of the simplest methods to construct cyclic ethers or
lactones.
C.-G. Yang, N. W. Reich, Z. Shi, C. He, Org. Lett.,
2005, 7, 4553-4556.
A new copper-catalyzed oxidative [3 + 2] cycloaddition of alkenes with
anhydrides using oxygen as the sole oxidant affords γ-lactones in good to
excellent yield. This catalyzed cyclization process has a broad substrate scope.
L. Huang, H. Jiang, C. Qi, X. Liu, J. Am. Chem. Soc., 2010,
132, 17652-17654.
A new and reliable method for the direct construction of biologically important
aryl lactones and phthalides from carboxylic and benzoic acids is based on
selective benzylic C-H abstraction in the presence of hypervalent iodine(III)
reagents and KBr.
T. Dohi, N. Takenaga, A. Goto, A. Maruyama, Y. Kita, Org. Lett., 2007,
9, 3129-3132.
The hypervalent iodine reagent PIFA promotes the efficient intramolecular
electrophilic cyclization of easily accessible alkynylamides and alkynyl
carboxylic acids, leading to pyrrolidinone and lactone skeletons, respectively.
A synthetic study and a mechanistic proposal for these transformations are
presented.
I. Tellitu, S. Serna, M. T. Herrero, I. Moreno, E. Domínguez, R. SanMartin, J. Org. Chem., 2007,
72, 1526-1529.
Homogeneous carboamination, carboalkoxylation and carbolactonization of terminal
alkenes are realized via oxidative gold catalysis, providing expedient access to
various substituted N- or O-heterocycles. Deuterium-labeling studies established
the nature of the alkene functionalization and the indispensible role of Au(I)/Au(III)
catalysis.
G. Zhang, L. Cui, Y. Wang, L. Zhang, J. Am. Chem. Soc., 2010,
132, 1474-1475.
Several Pd-catalyzed oxidative cyclizations proceed in excellent yield under
simple aerobic conditions. Importantly, this system provided entry into
enatioselective catalysis with a readily available Pd-sparteine complex.
R. M. Trend, Y. K. Ramtohul, E. M. Ferreira, B. Stoltz,
Angew. Chem. Int. Ed., 2003, 42, 2892-2895.
In the presence of CuI/trans-N,N′-dimethylcyclohexane-1,2-diamine as
catalyst, a number of carboxylic acids underwent efficient intramolecular O-vinylation
with vinyl bromides leading to the corresponding five- and six-membered enol
lactones. The same catalytic system also enabled an efficient cycloisomerization
of alkynoic acids.
C. Sun, Y. Fang, S. Li, Y. Zhang, Q. Zhao, S. Zhu, C. Li, Org. Lett., 2009,
11, 4084-4087.
C. Sun, Y. Fang, S. Li, Y. Zhang, Q. Zhao, S. Zhu, C. Li, Org. Lett., 2009,
11, 4084-4087.
A general, efficient, and convenient cyclization of alkynes bearing carboxylic
acids to the corresponding γ-alkylidene-γ-butyrolactones in the presence of
commercially available Au2O3 shows a high degree of
chemo-, regio-, and stereoselectivity. The 5-exo mode of cyclization and anti
auration are a general trend for the Au2O3 catalyst.
P. Y. Toullec, E. Genin, S. Antoniotti, J.-P. Genęt, V. Michelet, Synlett, 2008,
707-711.
A highly efficient gold-catalyzed cyclization reaction of various
functionalized acetylenic leads to γ-lactones in good to excellent yields.
The reaction conditions are compatible with several functional groups, such
as ester, alkene, alkyne, chloro, and free or protected alcohol.
E. Genin, P. Y. Toullec, S. Antioniotti, C. Brancour, J.-P. Genęt, V.
Michelet, J. Am. Chem. Soc.,
2006, 128, 3112-3113.
Imidazolinium-derived carbenes catalyze an efficient ring-expansion
lactonization of oxacycloalkane-2-carboxaldehydes to give various functionalized
five-, six-, and seven-membered lactones under mild reaction conditions. The
electronic nature of the carbene catalyst plays a crucial role for the success
of this method.
L. Wang. K. Thai, M. Gravel, Org. Lett., 2009,
11, 891-893.
A mechanistic investigation on the effect of substrate on stereoselectivity in the triflic acid-catalyzed allylboration
reaction between 2-alkoxycarbonyl allylboronates and aldehydes confirms the
involvement of a carbocation intermediate as the source of stereochemical
inversion. This methodology allows a facile access to β,γ-disubstituted
five-membered ring lactones.
T. G. Elford, Y. Arimura, S. H. Yu, D. G. Hall, J. Org. Chem., 2007,
72, 1276-1284.
T. G. Elford, Y. Arimura, S. H. Yu, D. G. Hall, J. Org. Chem., 2007,
72, 1276-1284.
Depending on the strength of a Lewis or Brřnsted acid catalyst, borate intermediates resulting from the crotylboration of aliphatic aldehydes
with ester-containing crotylboronates form either γ-substituted-α-alkylidene-γ-butyrolactones
via oxonia cope
rearrangement-lactonization or
β,γ-disubstituted-α-methylene-γ-butyrolactones via lactonization.
P. V. Ramachandran, D. Pratihar, Org. Lett., 2007,
9, 2087-2090.
P. V. Ramachandran, D. Pratihar, Org. Lett., 2007,
9, 2087-2090.
The Reformatsky reaction of α-hydroxy ketones with indium enolates furnished
highly diastereoselective lactones, while α-alkoxy ketones gave acyclic
esters in moderate selectivities. A boat-type of chelated bicyclic
transition state involving highly diastereoselective construction of three
contiguous stereogenic centers is proposed.
S. A. Babu, M. Yasuda, Y. Okabe, I. Shibata, A. Baba, Org. Lett.,
2006, 8, 3029-3032.
Treatment of 3-[(alkoxycarbonyl)alkyl]-substituted conjugated cycloalkenones
with diisobutylaluminum hydride at -78 °C followed by acid quenching
furnishes spiro ethers, whereas the corresponding 3-(carboxyalkyl)-substituted
cycloalkenones generate spiro lactones upon reaction with sodium borohydride
at 30 °C followed by acid quenching.
M.-C. P. Yeh, Y.-C. Lee, T.-C. Young, Synthesis, 2006, 3621-3624.
A mild, enantioselective
hetero-Diels-Alder (HDA) reaction of the Brassard diene with aldehydes in the
presence of a chiral titanium(IV) tridentate Schiff-base complexe has been
developed. The
mechanism is discussed.
Q. Fan, L. Lin, J. Liu, Y. Huang, X. Feng, Eur. J. Org. Chem., 2005,
3542-3552.
The Brřnsted acid catalyzed formal insertion of an isocyanide into a C-O bond
of various acyclic and cyclic acetals can be applied to form α-alkoxy imidates.
Functional groups, such as nitro, cyano, halogen, ester, and alkoxy groups, are
tolerant to the reaction conditions employed. The course of the reaction is
highly dependent on the structure of the isocyanide.
M. Tobisu, A. Kitajima, S. Yoshioka, I. Hyodo, M. Oshita, N. Chatani, J. Am. Chem. Soc.,
2007,
129, 11431-11437.
The synthesis of a planar-chiral bisflavin catalyst (1) and its use
in asymmetric Bayer-Villiger-Oxidations is described.
S. Murahashi, S. Ono, Y. Imada, Angew. Chem. Int. Ed., 2002, 41,
2366-2368.
A quinine tethered Co(III)-salen complex promotes as a Lewis acid-Lewis base
(LA*-LB*) bifunctional catalyst a rapid asymmetric [2+2] cycloaddition reaction
between ketene and aldehydes to produce C4-substituted β-lactones in uniformly
>99% ee and high isolated yields.
S. Chidara, Y.-M. Lin, Synlett, 2009,
1675-1679.
Chiral N-hetereocyclic carbenes are efficient catalysts for the formal [2 + 2]
cycloaddition reactions of alkyl(aryl)ketenes with 2-oxoaldehydes to afford
highly substituted β-lactones in high yields with good diastereoselectivities
and excellent enantioselectivities. Both alkyl(aryl)ketenes and diarylketene
worked well in this reaction.
L. He, H. Lv, Y.-R. Zhang, S. Ye, J. Org. Chem., 2008,
73, 8101-8103.
The regioselective opening of Bn2N-α-methylserine-β-lactone
with organocuprates gave enantiopure α-methyl amino acids in excellent yields.
N. D. Smith, A. M. Wohlrab, M. Goodman, Org. Lett., 2005, 7, 255-258.
A new Pd-catalyzed oxidation reaction for the stereospecific conversion of
enynes into cyclopropyl ketones proceeds with net inversion of geometry with
respect to the starting olefin. This result is consistent with a mechanism in
which the key cyclopropane-forming step involves nucleophilic attack of a
tethered olefin onto the PdIV-C bond.
L. L. Welbes, T. W. Lyons, K. A. Cychosz, M. S. Sanford, J. Am. Chem. Soc., 2007,
129, 5836-5837.
