Categories: C-C Bond Formation > Carbocyclic compounds > Cycloalkenes
Synthesis of cyclopentenes
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Recent Literature
The reaction of organocerium reagents, generated in situ from aryl and
heteroaryl lithium compounds, with cycloalkanones proceeds cleanly to provide
alkoxides. Addition of MsCl or SOCl2 with DBU gave aryl-substituted
cycloalkenes in good yields. A short total synthesis of (±)-laurokamurene B is
described.
J. Tallineau, G. Bashiardes, J.-M. Coustard, F. Lecornué, Synlett, 2009,
2761-2764.
The facile preparation of organoboronates and their remarkable stability and
functional group tolerance enable straightforward syntheses of four- and
five-membered carbo- and heterocycles via in situ transmetalation of sensitive
organometallics with boron alkoxides.
A. N. Baumann, M. Eisold, A. Music, D. Didier, Synthesis, 2018, 50,
3149-3160.
In situ generation of allylic boronates by iridium-catalyzed borylation of
cyclic alkenes in the presence of additives, such as methylimidazole and DBU,
followed a reaction with aldehydes allows the synthesis of stereodefined
homoallylic alcohols. Cycloalkenes without additives as well as acyclic
substrates gave vinylic boronates, which were coupled with organohalides in a
Suzuki-Miyaura sequence.
V. J. Olsson, K. J. Szabó, J. Org. Chem., 2009,
74, 7715-7723.
V. J. Olsson, K. J. Szabó, J. Org. Chem., 2009,
74, 7715-7723.
A new phosphoramidite is an effective chiral ligand in a palladium-catalyzed
asymmetric Mizoroki-Heck reaction using benzyl electrophiles. The reaction is
compatible with polar functional groups and can be readily scaled up. Several
cyclic olefins worked well as olefin components.
Z. Yang, J. Zhou, J. Am. Chem. Soc., 2012,
134, 11833-11835.
In an asymmetric intermolecular Heck reaction, various cyclic olefins coupled
with aryl and vinyl bromides in high enantioselectivity. Only bisphosphine
oxides on a spiro backbone formed highly stereoselective Pd catalysts. The use
of alkylammonium salts and alcoholic solvents were essential to promote halide
dissociation from the arylpalladium intermediate.
C. Wu, J. Zhou, J. Am. Chem. Soc., 2014,
136, 650-652.
Asymmetric allylic substitution with organolithium reagents enables a highly
regio- and enantioselective desymmetrization of meso-1,4-dibromocycloalk-2-enes
to afford enantioenriched bromocycloalkenes. The cycloheptene products undergo
an unusual ring contraction.
S. S. Goh, S. Guduguntly, T. Kikuchi, M. Lutz, E. Otten, M. Fujita, B. L.
Feringa, J. Am. Chem. Soc.,
2018,
140, 7052-7055.
Cycloalkenes can be efficiently prepared by a new Ru-catalyzed decarbonylative
cyclization of terminal alkynals. Under appropriate conditions,
cycloisomerizations to conjugated aldehydes may be observed. Both processes
involve catalytic Ru vinylidenes.
J. A. Varela, C. González-Rodríguez, S. G. Rubín, L. Castedo, Carlos Saá, J.
Am. Chem. Soc., 2006, 128, 9576-9577.
A 1:1 mixture of the (π-allyl)palladium complex (η3-C3H5)Pd(Cl)PCy3
and NaB[3,5-C6H3(CF3)2]4
catalyzed the cycloisomerization of functionalized 1,6-dienes in the presence of
HSiEt3 to provide 1,2-disubstituted cyclopentenes in good yield.
R. A. Widenhoefer, N. S. Perch,
Org. Lett., 1999, 1, 1103-1105.
Cationic palladium phenanthroline complexes catalyze the cycloisomerization of functionalized
1,5- and 1,6-dienes to form cyclopentenes which possess a trisubstituted olefin in good yield and with good
selectivity.
P. Kisanga, L. A. Goj, R. A. Widenhoefer, J. Org. Chem., 2001,
66, 635-637.
Iridium complexes also catalyze the cycloisomerization of enynes. The reaction
patterns depend on the structure of the substrates and the nature of the
catalyst systems.
N. Chatani, H. Inoue, T. Morimoto, T. Muto, S. Murai, J. Org. Chem., 2001,
66, 4433-4436.
A metal-free oxidative decarbonylative [3+2] annulation of terminal
alkynes with tertiary γ,δ-unsaturated aldehydes provides cyclopentenes, whereas
the reaction of terminal alkynes with 2-methyl-2-arylpropanals provides indenes.
The reactions offer broad substrate scope and excellent selectivity.
H.-X. Zou, Y. Li, X.-H. Yang, J. Xiang, J.-H. Li, J. Org. Chem., 2018, 83,
8581-8588.
Copper-catalyzed arylcarbocyclization of alkynes with diaryliodonium salts
provides carbocycles with good step-economy through C-C bond formation on an
inert C(sp3)-H bond. Theoretical studies revealed an interesting
Cu-catalyzed concerted pathway of the C-C bond formation.
J. Peng, C. Chen, J. Chen, X. Su, C. Xi, H. Chen, Org. Lett., 2014,
16, 3776-3779.
A combination of B(C6F5)3, an N-alkylamine
and a BOX-ZnI2 complex catalyzes an efficient and highly
enantioselective Conia-ene-type process. Through cooperative action of B(C6F5)3
and amine, ketones can be converted in situ to the corresponding enolates. A
subsequent enantioselective cyclization involving a BOX-ZnI2-activated
alkyne provides various cyclopentenes in very good yield.
M. Cao, A. Yesilcimen, M. Wasa, J. Am. Chem. Soc.,
2019,
141, 4199-4203.
A highly enantioselective Rh-catalyzed asymmetric allylic substitution allows
the desymmetrization of meso cyclopent-2-ene-1,4-diethyl dicarbonates.
Depending on the ligand, each of two regioisomeric products can be obtained in
good yield and excellent enantioselectivity. Whereas bisphosphine P-Phos ligands
form trans-1,2-arylcyclopentenols, Segphos ligands lead predominantly to
trans-1,4-arylcyclopentenols.
F. Menard, D. Perez, D. S. Roman, T. M. Chapman, M. Lautens, J. Org. Chem., 2010,
75, 4056-4068.
A Highly Stereospecific Claisen-Sakurai Approach to Densely Functionalized
Cyclopentenols
K. S. Stankevich, M. J. Cook, J. Org. Chem., 2022, 87,
12250-12256.
Copper-catalyzed [3 + 2] cycloadditions of N-tosylcyclopropylamine
with alkynes and alkenes under visible light irradiation provide diversified
aminated cyclopentene and cyclopentane derivatives being relevant for drug
synthesis. The protocol is operationally simple, economically affordable, and
compatible with a range of functionalities.
M. Kumar, S. Verma, V. Mishra, O. Reiser, A. K. Verma J. Org. Chem., 2022, 87,
6263-6272.
A P-cyclohexyl substituted ferrocenophane catalyst affords high levels of
asymmetric induction in the organocatalytic [3 + 2] annulation reaction between
allenes and electron-poor olefins.
A. Voituriez, A. Panossian, N. Fleury-Brégeot, P. Retailleau, A. Marinetti, J. Am. Chem. Soc., 2008,
130, 14030-14031.
A nucleophile-catalyzed asymmetric [3+2] cycloaddition of allenes with enones is
described. The method has also been applied to reactions of trisubstituted
olefins, thereby generating quartenary and tertiary stereocenters.
J. E. Wilson, G. C. Fu, Angew. Chem. Int. Ed., 2006, 45,
1426-1429.
The GaCl3-catalyzed skeletal reorganization of enynes is simple and
provides a diverse range of dienes in good to high yields. The reaction of
enynes proceeds in a stereospecific manner with respect to the geometry of the
olefin moiety.
N. Chatani, H. Inoue, T. Kotsuma, S. Murai, J. Am. Chem. Soc., 2002,
124, 10294-10295.
n the presence of a catalytic amount of Pd(TFA)2 and a chiral
Pyox ligand, an oxidative Heck reaction between arylboronic acids and
4-substituted or 4,4-disubstituted cyclopent-1-enes provides arylated products
with concurrent creation of two stereocenters in good yields with excellent
diastereo- and enantioselectivities under an atmosphere of oxygen.
G. Chen, J. Cao, Q. Wang, J. Zhu,
Org. Lett., 2020, 22, 322-325.
An allylic alkylation/ring-closing metathesis domino process is catalyzed by the
combination of a palladium and a ruthenium catalyst. This study demonstrates the
compatibility of the two catalytic systems. Evidence for Grubbs' catalysts
activity in allylic alkylation is also reported.
C. Kammerer, G. Prestat, T. Gaillard, D. Madec, G. Poli, Org. Lett., 2008,
10, 405-408.
Palladium-catalyzed annulation reactions of conjugate acceptors and allenyl
boronic ester provide substituted cyclopentenes in high yields and
diastereoselectivities, including polycyclic lactone and lactam products.
Reactions are hypothesized to initiate by conjugate addition of a nucleophilic
propargylpalladium complex.
B. L. Kohn, E. R. Jarvo, Org. Lett., 2011,
13, 4858-4861.
An efficient method allows a stereospecific synthesis of trans-substituted
cyclopentene derivatives via the ring-opening rearrangement of readily available
MCP alkenyl derivatives in good yields. This transformation might proceed
through a fast concerted pericyclic process rather than a simple radical pathway
or an ionic pathway.
X.-Y. Tang, M. Shi, J. Org. Chem., 2010,
75, 902-905.
An efficient cycloallylation of mono-enone mono-allylic carbonates is achieved
upon exposure to tributylphosphine and 1 mol % Pd(Ph3P)4.
This transformation combines the nucleophilic features of the
Morita-Baylis-Hillman reaction with the electrophilic features of the
Trost-Tsuji reaction.
B. G. Jellerich, J.-R. Kong, M. J. Krische, J. Am. Chem. Soc., 2003,
125, 7758-7759.
Using a catalytic amount of trialkylphosphines, alkyl halides undergo
efficient intramolecular Morita-Baylis-Hillman cyclization.
M. E. Krafft, K. A. Seibert, Synlett, 2006,
3334-3336.
An organomediated, intramolecular Morita-Baylis-Hillman reaction of molecules
bearing allylic leaving groups as the electrophilic partner provided a facile,
high yielding, straightforward synthesis of densely functionalized cyclic
molecules.
M. E. Krafft, T. F. N. Haxell, J. Am. Chem. Soc., 2005, 127,
10168-10169.
Conversion of unsaturated ketones and aldehydes derived from the
cycloisomerization of primary and secondary propargyl diynols in the presence of
[CpRu(CH3CN)3]PF6 to 1-azatrienes and a
subsequent electrocyclization-dehydration provides pyridines with excellent
regiocontrol.
B. M. Trost, A. C. Gutierrez, Org. Lett., 2007,
9, 1473-1476.
An enantioselective synthesis of α,α-disubstituted cyclopentenes proceeds via a
chiral enol generated in situ from an α,β-unsaturated aldehyde and a chiral N-heterocyclic
carbene catalyst. This reactive enol undergoes addition to one of two
enantiotopic ketones to afford an optically active β-lactone. Depending on the
substitution, a decarboxylation produces the cyclopentene products in high ee.
M. Wadamoto, E. M. Philipps, T. E. Reynolds, K. A. Scheidt, J. Am. Chem. Soc.,
2007,
129, 10098-10099.
An oxidation-methylenation one-pot procedure in the presence different catalysts
produced terminal alkenes in high yields. A methylenation-ring-closing process
for the synthesis of cyclic alkenes from carbonyl derivatives was even expanded
with an initial oxidation to allow the use of alcohols as substrates.
H. Lebel, V. Paquet, J. Am. Chem. Soc., 2004, 126,
11152-11153.
N-Heterocyclic carbene/Lewis acid cooperative catalysis provides access
to cis-1,3,4-trisubstituted cyclopentenes from enals and chalcone
derivatives with high levels of diastereoselectivity and enantioselectivity. The
presence of Ti(OiPr)4 as Lewis acid enables an efficient
substrate preorganization, which translates into high levels of
diastereoselectivity.
B. Cardinal-David, D. E. A. Raup, K. A. Scheidt, J. Am. Chem. Soc., 2010,
132, 5345-5347.
Ruthenium carbene complexes catalyze ring closing metathesis (RCM) and a
subsequent hydrogenation after activation with sodium hydride. Hydrogenation of
cyclopentenols proceeds smoothly at ambient temperature and under 1 atm of
hydrogen in toluene.
B. Schmidt, M. Pohler, Org. Biomol. Chem., 2003, 1,
2512-2517.
J. A. Varela, C. González-Rodríguez, S. G. Rubín, L. Castedo, Carlos Saá, J.
Am. Chem. Soc., 2006, 128, 9576-9577.
TFA-promoted exo carbocyclizations of nonterminal alkynals gave good to
excellent yields of exo cycloalkenones. On the other hand, terminal
5-alkynals gave endo carbocyclizations to cyclohexenones. These
carbocyclizations can be considered as tandem alkyne hydration/aldol
condensation processes.
C. González-Rodríguez, L. Escalante, J. A. Varela, L. Castedo, C. Sáa, Org. Lett., 2009,
11, 1531-1533.
Triflyl nitrate is an effective nitrating agent for a wide range of
unsaturated substrates to form nitro olefins. The reagent is easily generated from tetra-n-butylammonium nitrate in
CH2Cl2 solution.
G. S. Reddy, E. J. Corey, Org. Lett., 2021, 23,
3379-3383.
A sequence of Pd-catalyzed haloallylation of alkynes, Pd-catalyzed
cross-coupling, and Ru-catalyzed ring-closing metathesis enables a short
approach to various 1,2-disubstituted cyclopentadienes. The scope of the method
is broad.
N. Topolovčan, I. Panov, Martin Kotora, Org. Lett.,
2016, 18, 3634-3637.
Trapping of β,γ-alkynyl aldehydes, generated in situ by treatment of alkynyloxiranes with a
catalytic amount of Sc(OTf)3 or BF3·OEt2, by a variety of allyl nucleophiles affords homopropargylic
homoallylic alcohols in good yield and selectivity. Subsequent enyne metathesis
gives functionalized vinylcyclopentenols.
L. Wang, M. L. Maddess, M. Lautens, J. Org. Chem., 2007,
72, 1822-1825.
The use of cationic silver (AgSbF4) as a catalyst for intra- and
intermolecular alkyne-carbonyl coupling is described.
J. U. Rhee, M. J. Krische, Org. Lett., 2005, 7, 2493-2495.
Iodocyclopentenes are formed at room temperature upon
iodonium-promoted 5-endo-dig carbocyclization of
δ-alkynyl-β-ketoesters with I2. Cyclizations
involving terminal and substituted (alkyl, aryl, Br, I) alkynes were accessed.
J. Barluenga, D. Palomas, E. Rubio, J. M. Gonzáles, Org. Lett., 2007,
9, 2823-2826.
A sequence of two gold(I)-catalyzed isomerization steps allows the synthesis of
functionalized acetoxy bicyclo[3.1.0]hexenes from 5-en-2-yn-1-yl acetates.
Acetoxy bicyclo[3.1.0]hexene products can be further transformed to
2-cycloalkenones by simple methanolysis.
A. Buzas, F. Gagosz, J. Am. Chem. Soc., 2006, 128,
12614-12615.