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Synthesis of 1,4-dienes
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Tributylmagnesate (nBu3MgLi) and the more
reactive dibutylisopropylmagnesate (iPrnBu2MgLi)
induce facile iodine/bromine-magnesium exchange to provide various
polyfunctionalized arylmagnesium species. The exchange of alkenyl halides using
this method proceeds with retention of configuration of the double bond.
A. Inoue, K. Kitagawa, H. Shinokubo, K. Oshima, J. Org. Chem., 2001,
66, 4333-4339.
In situ generated palladium(0) nanoparticles catalyze an efficient
cross-coupling of allyl acetates with aryl and vinyl siloxanes. The reactions
are stereoselective, and linear (E)-coupling products are obtained both
from cis and trans allyl acetates. The coupling with vinyl
siloxanes provides a novel protocol for the synthesis of 1,4-pentadienes.
R. Dey, K. Chattopadhyay, B. C. Ranu, J. Org. Chem., 2008,
73, 9461-9464.
Alkenyltrifluoroborates can be cross-coupled
with allyl and benzyl chlorides using KOH as base in acetone-water (3:2) at 50
°C and low catalyst loadings of a 4-hydroxyacetophenone oxime derived
palladacycle giving the corresponding 1,4-dienes and allylarenes, respectively.
The use of overheated water as solvent and K2CO3 as base
allows a coupling of alkenyltrifluoroborates with aryl and heteroaryl
bromides.
E. Alacid, C. Nájera, J. Org. Chem., 2009,
74, 2321-2327.
A microwave synthesis of 1,4-pentadienes has been developed involving the
palladium-catalyzed cross-coupling of potassium vinyltrifluoroborates with
allyl acetates.
G. W. Kabalka, M. Al-Masum, Org. Lett.,
2006,
8, 11-13.
A cross-coupling reaction of allylic and benzylic carbonates with organo[2-(hydroxymethyl)phenyl]dimethylsilanes
proceeds in the presence of a palladium catalyst and in the absence of any
activator. Various functional groups are tolerated to give a diverse range of
1,4-diene and diarylmethane products.
Y. Nakao, S. Ebata, J. Chen, H. Imanaka, T. Hiyama, Chem. Lett., 2007,
606-607.
The hydroallylation of terminal alkyl and aryl alkynes with simple allyl
phosphates and 2-substituted allyl phosphates provides skipped dienes. The
hydroallylation of functionalized internal alkynes enables the synthesis of
complex trisubstituted alkenes.
M. Mailig, A. Hazra, M. K. Armstrong, G. Lalic, J. Am. Chem. Soc., 2017,
139, 6969-6977.
A nickel-catalyzed direct reaction of allylic alcohols with easily accessible
alkenyl boronates provides valuable 1,4-dienes with high regio- and
stereoselectivity in good to excellent yields, wide substrate scope, and
functional group compatibility. The proper choice of ancillary ligands is highly
important for this reaction.
X. Wu, M. Yang, Y. Liu, Org. Lett., 2023, 25,
8782-8786.
A CO2-promoted and Ni-catalyzed direct hydroallylation of terminal alkynes with
allylic alcohols provides 1,4-dienes in
good yield with excellent Markovnikov selectivity for alkyl- and
aryl-substituted terminal alkynes under mild reaction conditions.
Z. Zhang, D. Li, C. Xi, Org. Lett., 2023, 25,
698-702.
An enhanced Lewis acid system of InCl3 and Me3SiBr can be used to promote a
wide range of direct coupling reactions between alcohols and silyl nucleophiles
in non-halogenated solvents. Highly chemoselective allylations toward a hydroxyl
moiety over ketone and acetoxy ones have been demonstrated.
T. Saito, Y. Nishimoto, M. Yasuda, A. Baba, J. Org. Chem., 2006,
71, 8516-8522.
A Pd(0)-catalyzed allylic cross-coupling of homoallylic tosylate substrates
with boronic acids and pinacol esters uses 2-(4,5-dihydro-2-oxazolyl)quinoline
(quinox) as a ligand and is performed at ambient temperature. The scope of the
reaction is broad in terms of both the boronate and the tosylate, that includes
secondary tosylates.
B. J. Stokes, S. M. Opra, M. S. Sigman, J. Am. Chem. Soc., 2012,
134, 11408-11411.
The reaction of an allyl titanium reagent prepared from
1-phenylthio-4-trimethylsilyl-2-butene with a ketone provides a tertiary
alcohol, that undergoes a Brřnsted acid-mediated rearrangement reaction to
generate a geminal divinyl compound.
R. Ogura, K. Satoh, W. Kiuchi, K. Kato, K. Ikeuchi, T. Suzuki, K. Tanino, Org. Lett.,
2022, 24, 5041-5044.
A direct Ir-catalyzed asymmetric substitution reaction between branched, racemic
allylic alcohols and potassium alkenyltrifluoroborates proceeded with high site
selectivity and excellent enantioselectivity. This method allows rapid access to
various 1,4-dienes or trienes including the biologically active natural products
(-)-nyasol and (-)-hinokiresinol.
J. Y. Hamilton, D. Sarlah, E. M. Carreira, J. Am. Chem. Soc., 2013,
135, 994-997.
Enantioselective allylic additions of alkenyl units to readily accessible
allylic electrophiles afford 1,4-dienes that contain a tertiary carbon
stereogenic site in the presence of a copper complex of a chiral N-heterocyclic
carbene (NHC). Aryl- as well as alkyl-substituted electrophiles bearing a di- or
trisubstituted alkene may be employed. Reactions can involve a variety of robust
alkenyl-(pinacolatoboron) compounds.
F. Gao, J. L. Carr, A. H. Hoveyda, J. Am. Chem. Soc., 2014,
136, 2149-2161.
A nickel-catalyzed direct reaction of allylic alcohols with easily accessible
alkenyl boronates provides valuable 1,4-dienes with high regio- and
stereoselectivity in good to excellent yields, wide substrate scope, and
functional group compatibility. The proper choice of ancillary ligands is highly
important for this reaction.
X. Wu, M. Yang, Y. Liu, Org. Lett., 2023, 25,
8782-8786.
A nickel-catalyzed cross-coupling of allyl alcohols with aryl- and alkenylzinc
chlorides provides linear cross-coupling products.
B. Yang, Z.-X. Wang, J. Org. Chem.,
2017, 82, 4542-4549.
The Suzuki-Miyaura cross-coupling with chiral γ,γ-disubstituted allylboronates
provides nonracemic compounds with quaternary centers with high regioselectivity
and enantiospecificity in the presence of RuPhos ligand. The reaction occurs by
transmetalation with allyl migration, followed by rapid reductive elimination.
B. Potter, E. K. Edelstein, J. P. Morken, Org. Lett.,
2016, 18, 3286-3289.
A nickel-catalyzed coupling of enones or enals with alkynes in the presence
of silane and titanium alkoxide reductants provides direct access to skipped
diene products via a net four-electron reductive coupling and deoxygenation. A new class of
well-defined nickel(0) precatalysts bearing an unhindered N-heterocyclic carbene
ligand is essential for the
efficiency of the transformation.
D. P. Todd, B. B. Thompson, A. J. Nett, J. Montgomery, J. Am. Chem. Soc., 2015,
137, 12788-12791.
A mild, cobalt-catalyzed 1,4-hydrovinylation of acyclic 1,3-dienes with
various functionalized terminal alkenes is described. Unsymmetrical
1,3-dienes yield products, where the new carbon-carbon bond is formed at the
less substituted end of the 1,3-diene.
G. Hilt, S. Lüers, Synthesis,
2002, 609-618.
In cobalt-catalyzed 1,4-hydrovinylation, dppe/dppp ligands led to the formation
of the branched product, whereas the SchmalzPhos ligand generates the
corresponding linear product in both excellent yields and regioselectivities.
The catalyst exhibits a high tolerance toward functional groups, and the very
mild reaction conditions allow the synthesis of 1,4-dienes without isomerization
into conjugated systems.
M. Arndt, M. Dindaroğlu, H.-G. Schmalz, G. Hilt, Org. Lett., 2011,
13, 6184-6187.
Monosubstituted acyclic (E)-1,3-dienes undergo efficient hydrovinylation
giving (Z)-3-alkylhexa-1,4-dienes upon treatment with catalytic amounts
of bidentate phosphine-CoCl2 complexes and Me3Al in an
atmosphere of ethylene. Complexes derived from (RR)-DIOP and (SS)-BDDP
at -45°C give very high enantioselectivities for several prototypical
1,3-dienes.
R. K. Sharma, T. V. RajanBabu, J. Am. Chem. Soc., 2010,
132, 3295-3297.
A nickel-catalyzed intermolecular process for direct allylation of nonconjugated,
nonstrained simple alkenes affords the desired linear 1,4-dienes in high yield
in both gram-scale and smaller scale coupling reactions.
R. Matsubara, T. F. Jamison, J. Am. Chem. Soc., 2010,
132, 6880-6881.
Sulfonate bearing chiral bidentate N-heterocyclic carbene (NHC) complexes
promote catalytic enantioselective allylic substitution reactions, which involve
the use of alkyl- or aryl-substituted vinylaluminum reagents and afford
1,4-dienes containing a quaternary carbon stereogenic center at their C-3 site.
F. Gao. K. P. McGrath, Y. Lee, A. H. Hoveyda, J. Am. Chem. Soc., 2010,
132, 14315-14320.
Vinylaluminum reagents prepared from the reaction of commercially available
DIBAL-H and a terminal alkyne can be used directly without purification in
catalytic asymmetric allylic alkylation reactions with allylic phosphates in the
presence of a readily available chiral N-heterocyclic carbene (NHC)
complex and a commercially available and air stable Cu salt.
Y. Lee, K. Akiyama, D. G. Gillingham, M. Kevin Brown, A. H. Hoveyda, J. Am. Chem. Soc., 2008,
130, 446-447.
A regio- and stereoselective nickel-catalyzed three-component coupling
reaction of aldehydes, 1,3-dienes, and alkenylzirconium afforded skipped diene
compounds bearing various functionals and heterocyclic groups. The products were
readily transformed into structurally diverse polyenes.
C.-G. Wang, Y. Zhang, S. Wang, B. Chen, Y. Li, H.-L. Ni, Y. Gao, P. Hu, B.-Q.
Wang, P. Cao, Org. Lett., 2021, 23,
535-541.
Treatment of (Z)-γ-trimethylsilyl allylic alcohols with a catalytic or
stoichiometric amount of lithium tert-butoxide provides cyclic silyl
ethers. A subsequent reaction with allylic halides followed by
tetrabutylammmonium fluoride assisted hydrolysis produces 2,5-alkadien-1-ols
with complete retention of configuration of the double bond.
H. Taguchi, K. Ghoroku, M. Tadaki, A. Tsubouchi, T. Takeda, Org. Lett., 2001, 3,
3811-3814.
Sigmatropic rearrangement of allenyl ethers furnishes α,β-unsaturated
aldehydes in good yield.
P. J. Parsons, P. Thomson, A. Taylor, T. Sparks,
Org. Lett., 2000, 2, 571-572.
Ketone-stabilized phosphonium ylides were allylated with high regioselectivity
by primary allylic amines in the presence of 5 mol % Pd(PPh3)4
and 10 mol % B(OH)3. A subsequent one-pot Wittig olefination gave
structurally diverse α,β-unsaturated ketones in good to excellent overall yields.
Ester- and nitrile-stabilized phosphonium ylides can be converted if B(OH)3
is replaced with TsOH.
X.-T. Ma, Y. Wang, R.-H. Dai, C.-R. Liu, S.-K. Tian, J. Org. Chem., 2013,
78, 11071-11075.
A practical, highly enantioselective reaction of readily available 1,3-dienes
and alkyl acrylates provides valuable, enantio-pure skipped 1,4-diene esters in
the presence of commercially available cobalt salts and chiral ligands. This
hetero-dimerization reaction tolerates various organic functional groups (e.g.,
aromatic substituents, halides, isolated mono- and di-substituted double bonds,
esters, silyl ethers, and silyl enol ethers).
S. M. Jing, V. Balasanthiran, V. Pagar, J. C. Gallucci, T. V. Rajanbabu, J. Am. Chem. Soc., 2017,
139, 18034-18043.
An iridium-catalyzed allylic alkylation of phosphonates followed by a
Horner-Wadsworth-Emmons olefination provides skipped dienes bearing a C3
stereogenic center, generally with outstanding enantioselectivities.
A. Seal, S. Mukherjee, Org. Lett., 2023, 25,
2253-2257.
A Ba/Pd cooperative catalysis system enables a dehydrative cross-coupling of
allylic alcohols with P-ylides followed by a Wittig reaction in one pot. Various
multisubstituted 1,4-dienes were isolated in very good yields with a broad range
of P-ylides and aldehydes with excellent E selectivity.
P. Xie, W. Fu, X. Cai, Z. Sun, Y. Wu, S. Li, C. Gao, X. Yang, T.-P. Loh,
Org. Lett., 2019, 21, 7055-7059.
An iridium-catalyzed directed olefinic C-H allylation and alkenylation of
NH-Ts acrylamides in water provides various 1,4- and 1,3-diene skeletons. This
practical and atom-economic reaction tolerated a wide scope of substrates under
simple reaction conditions and enabled successful gram-scale preparation.
Furthermore, an asymmetric synthesis of 1,4-dienes was achieved.
Y. Huang, L. Xu, F. Yu, W. Shen, X. Lu, L. Ding, L. Zhong, G. Zhong, J. Zhang, J. Org. Chem., 2020, 85,
7225-7237.
Use of copper(I) tert-butoxide and allylic halides enables the
substitution of the silyl group in vinylsilanes by an allylic group. This
synthetic application of a 1,3 Csp2-to-O silyl migration provides a
useful method for the generation of vinyl anion equivalents.
A. Tsubouchi, M. Itoh, K. Onishi, T. Takeda, Synthesis,
2004, 1504-1508.
An efficient synthetic method provides tri- and tetra-substituted allenes by the
reaction of allylindium reagents with 3°-propargyl alcohols. Allylindium
reagents are generated in situ from indium and allyl bromides.
K. Lee, P. H. Lee, Org. Lett., 2008,
10, 2441-2444.
Sulfonate-bearing chiral bidentate N-heterocyclic carbene (NHC) complexes of
copper enable catalytic enantioselective allylic substitutions of allylic
phosphonates with commercially available allenylboronic acid that result in addition of
an allenyl group and formation of tertiary or
quaternary C-C bonds in up to
95% yield, >98% SN2′ selectivity, and 98% ee.
B. Jung, A. H. Hoveyda, J. Am. Chem. Soc., 2012,
134, 1490-1493.
An asymmetric boronate addition to sulfonyl hydrazones catalyzed by chiral
biphenols provides enantioenriched allenes in a traceless Petasis reaction. The
resulting Mannich product from nucleophilic addition eliminates sulfinic acid,
yielding a propargylic diazene that performs an alkyne walk to afford the allene.
Two enantioselective approaches have been developed for the synthesis of allylic
hydroxyl allenes and 1,3-alkenyl allenes.
Y. Jiang, A. B. Diagne, R. J. Thomson, S. E. Schaus, J. Am. Chem. Soc., 2017,
139, 1826-1829.
On exposure to BuLi, 3-bromo-2-iodocyclopent-2-enol O-TBS ether
undergoes iodine-lithium permutation with complete regioselectivity.
Reaction with different electrophiles affords the corresponding
2-substituted-3-bromocyclopentenol derivatives. Subsequent bromo-lithium
exchange with t-BuLi, followed by reaction with an equal or different
electrophile, affords 2,3-disubstituted cyclopentenols.
M. Luparia, A. Vadalŕ, G. Zanoni, G. Vidari, Org. Lett.,
2006,
8, 2147-2150.