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Synthesis of 1,3-dienes
Lithiated allylic phosphonates undergo efficient olefination reactions with a variety of aldehydes in the presence of HMPA to give terminal 1,3-dienes with high selectivity for the E-isomer. This method is general and procedurally simple.
Y. Wang, F. G. West, Synthesis, 2002, 99-103.
A mild, base-free, and operationally straightforward Lewis acid-promoted addition of 1,3-bis(silyl)propenes to aldehydes provides the corresponding (E)-1,3-dienes in excellent stereoselectivity and good yields.
T. Borg, P. Tuzina, P. Somfai, J. Org. Chem., 2011, 76, 8070-8075.
The combination of a CoCl2 precatalyst with an amido-diphosphine-oxazoline ligand catalyzes the geometrical isomerization of E/Z mixtures of 1,3-dienes to afford (E) isomers in high stereoselectivity. This facile transformation offers a broad substrate scope with good functional group tolerance and could be scaled up to gram scale.
W. Wang, S. He, Y. Zhong, J. Chen, C. Cai, Y. Luo, Y. Xia, J. Org. Chem., 2022, 87, 4712-4723.
A cobalt-catalyzed multipositional isomerization of conjugated dienes is operationally simple and atom-economical using readily available starting materials with an E:Z mixture to access disubstituted 1,3-dienes with excellent yields and good E,E stereoselectivity. A mechanism via alkene insertion of cobalt hydride species and β-H elimination of a π-allyl cobalt intermediate is proposed.
J. Zhao, G. Xu, X. Wang, J. Liu, X. Ren, X. Hong, Z. Lu, Org. Lett., 2022, 24, 4592-4597.
N-sulfonyl imines undergo olefination reactions with various benzylidenetriphenylphosphoranes or allylidenetriphenylphosphoranes under mild reaction conditions to afford an array of both Z- and E-isomers of conjugated alkenes in good to excellent yields and with greater than 99:1 stereoselectivity depending on the N-sulfonyl group.
D.-J. Dong, H.-H. Li, S.-K. Tian, J. Am. Chem. Soc., 2010, 132, 5018-5020.
A new modification of Julia-Kocienski olefination reaction based on the use of cation-specific chelating agents yields 1,3-dienes with predictable (E/Z)-selectivity. The influence of the aldehyde structure on the (E/Z) selectivity is discussed.
F. Billard, R. Robiette, J. Pospíšil, J. Org. Chem., 2012, 77, 6358-6364.
A biphenyl-2-ylphosphine with a basic amino group at the 3′ position possesses orthogonally positioned "push" and "pull" forces, that enable a gold(I)-catalyzed soft propargylic deprotonation and permit the bridging of a difference of >26 pKa units (in DMSO) between a propargylic hydrogen and a protonated tertiary aniline. This design led to efficient isomerization of alkynes into versatile 1,3-dienes with synthetically useful scope under mild reaction conditions.
Z. Wang, Y. Wang, L. Zhang, J. Am. Chem. Soc., 2014, 136, 8887-8890.
Ruthenium hydrides promote the positional isomerization of 1,3-dienes into more highly substituted 1,3-dienes in a stereoconvergent manner. The reaction can also be conducted in one pot starting with an ene-yne metathesis of terminal alkynes and alkenes and a subsequent decomposition of the Grubbs catalyst into a ruthenium hydride, which promotes the dienyl isomerization.
J. R. Clark, J. R. Griffiths, S. T. Diver, J. Am. Chem. Soc., 2013, 135, 3327-3330.
Synthesis of 1,3-diene from alkyne and ethylene (1 atm) was improved using a ruthenium NHC carbene complex having a heterocyclic carbene as a ligand. Various 1,3-dienes could be synthesized from alkynes and ethylene.
K. Tonogakia, M. Mori, Tetrahedron Lett., 2002, 43, 2235-2238.
In reaction kinetics and mechanistic studies of ethylene-internal alkyne metathesis promoted by Piers’s catalyst, an inverse effect of ethylene on the reaction rate was found. Kinetic and mechanistic studies identify a ruthenacyclobutane as resting state. Preparative syntheses of several 2,3-disubstituted 1,3-butadienes were achieved at low ethylene pressures.
T. M. Gregg, J. B. Keister, S. T. Diver, J. Am. Chem. Soc., 2013, 135, 16777-16780.
A stereoselective synthesis of dienes from aldehydes and N-allylhydrazine derivatives offers high levels of (E)-stereoselectivity for a variety of substrates. Addition of a dienophile to the reaction mixture allows a one-flask diene synthesis-cycloaddition sequence.
D. A. Mundal, K. E. Lutz, R. J. Thomson, Org. Lett., 2009, 11, 465-468.
A unique palladium hydride complex generated from a simple Pd source and boric acid [B(OH)3] enables a redox neutral rearrangement of an allene to a 1,3-diene.
Y. Al-Jawaheri, M. Turner, M. C. Kimber, Synthesis, 2018, 50, 2329-2336.
The reaction of acetylated α-allenic alcohols with LiBr in the presence of 1.5 mol % of Pd(OAc)2 provides substituted (Z,E)-2-bromo-1,3-dienes in good yields with excellent diastereoselectivity. Both secondary and tertiary acetates as well as terminal and nonterminal allenes can be converted.
A. Horváth, J.-E. Bäckvall, J. Org. Chem., 2001, 66, 8120-8126.
An aza-Peterson olefination of N-phenyl imines or ketones with allyl- or benzyltrimethylsilane provides 1,3-dienes and stilbene derivatives in high yields. Silanes can be deprotonated using Schlosser's base.
T. K. Britten A. J. Basson, D. D. Roberts, M. G. McLaughlin, Synthesis, 2021, 53, 3535-3544.
Cross metathesis of terminal alkenes with methyl (2Z,4E)-hexadienoate and related dienyl esters promoted by the standard second-generation Grubbs-Hoveyda catalyst provides substituted (2Z,4E)-dienyl esters in good yields. A fluorous catalyst is used for separation and recovery in gram-scale reactions.
G. Moura-Letts, D. P. Curran, Org. Lett., 2007, 9, 5-8.
In the eliminative reaction of (E)-β-chlorovinyl ketones, Et3N as Brönsted base effected a soft α-vinyl enolization to afford cumulenol intermediates. Addition of a catalytic amount of a Lewis base (PPh3) initiated isomerization to 1,3-dienones in high yields. Furthermore, the introduction of a carbon-based nucleophile into the reaction mixture provided a highly efficient synthetic route to 2H-pyran-2-ones in one pot.
H. Y. Kim, K. Oh, Org. Lett., 2015, 17, 6254-6257.
A palladium-catalyzed allylic C-H oxidative allylation of sulfoxonium ylides provides conjugated dienones in good yields. This conversion offers mild reaction conditions, wide substrate scope, and excellent regioselectivity.
C. Li, M. Li, W. Zhong, Y. Jin, Y. Jin, J. Li, W. Wu, H. Jiang, Org. Lett., 2019, 21, 872-875.
The first allylic C-H olefination with α-diazo esters synergistically catalyzed by a palladium(II) complex and (salen)CrCl directly generates conjugated polyene derivatives in good yields and with excellent stereoselectivities.
P.-S. Wang, H.-C. Lin, X.-L. Zhou, L.-Z. Gong, Org. Lett., 2014, 16, 3332-3335.
A Rh(I)-catalyzed propargyl Claisen rearrangement followed by stereoselective hydrogen transfer enables the synthesis of functionalized (E,Z) dienals from propargyl vinyl ethers. Z-Stereochemistry of the first double bond suggests the involvement of a six-membered cyclic intermediate whereas the E-stereochemistry of the second double bond stems from the subsequent protodemetalation step giving an (E,Z)-dienal.
D. V. Vidhani, M. E. Krafft, I. V. Alabugin, Org. Lett., 2013, 15, 4462-4465.
Wittig Olefination between Phosphine, Aldehyde, and Allylic Carbonate: A General Method for Stereoselective Synthesis of Trisubstituted 1,3-Dienes with Highly Variable Substituents
R. Zhou, C. Wang, H. Song, Z. He, Org. Lett., 2010, 12, 976-979.
Cooperative catalysis of a chiral Pd(0) catalyst and a chiral Brřnsted acid enables an asymmetric regioselective asymmetric α-pentadienylation reaction of aldehydes with cyclopropylacetylene derivatives as pentadienylation reagents to afford. α-pentadienylated aldehydes in high yields and enantioselectivities as well as excellent E/Z ratios.
M.-S. Wu, Z.-Y. Han, L.-Z. Gong, Org. Lett., 2021, 23, 636-641.
A combination of chiral hydridopalladium and enamine catalysis enables an asymmetric α-allylation of aldehydes with alkynes. The ternary catalyst system, consisting of an achiral palladium complex, a primary amine, and a chiral phosphoric acid tolerates a wide scope of α,α-disubstituted aldehydes and alkynes and provides the corresponding allylation products in high yields and with excellent levels of enantioselectivity.
Y.-L. Su, L-L. Li, X.-L. Zhou, Z.-Y. Dai, P.-S. Wang, L.-Z. Gong, Org. Lett., 2018, 20, 2403-2406.
A versatile and operationally simple base-catalyzed multi-component domino reaction between α,β-unsaturated carbonyl compounds, aldehydes, and alcohols is described, providing a new efficient, and stereoselective one-pot preparation of trisubstituted alkenes and 1,3-dienes.
H. Habib-Zahmani, S. Hacini, C. Bories, J. Rodriguez, Synthesis, 2005, 2151-2156.
Hot water as a mildly acidic catalyst efficiently promoted 1,n-rearrangement (n = 3, 5, 7, 9) of allylic alcohols. In some cases, the rearrangement reactions joined isolated C-C double or triple bonds to generate conjugated polyene or enyne structure motifs. The polyene natural product navenone B has been constructed by iterative use of a Grignard reaction, a 1,3-rearrangement of the resulting allylic alcohol, and subsequent oxidation.
P.-F. Li, H.-L. Wang, J. Qu, J. Org. Chem., 2014, 79, 3955-3962.
A simple iridium/copper relay catalysis system enables a direct aerobic α,β-dehydrogenation of γ,δ-unsaturated amides and carboxylic acids to provide conjugated dienamides and dienoic acids in excellent yield. Instead of α-C-H metalation, this reaction proceeds by β-C-H activation, which results in enhanced α-acidity.
Z. Whang, Z. He, L. Zhang, Y. Huang, J. Am. Chem. Soc., 2018, 140, 735-740.
A highly stereoselective Rh(I)-catalyzed 1,3-acetoxyl rearrangement of 1,2-allen-3-yl carboxylates leads to 2-acetoxy-1,3(E)-alkadienes. Features of the reaction are a high catalytic efficiency, broad scope and excellent E-selectivity.
X. Zhang, C. Fu, S. Ma, Org. Lett., 2011, 13, 1920-1923.
A gold(I)-catalyzed rearrangement of diversely substituted allenyl carbinol esters allows the efficient, rapid, and stereoselective synthesis of various functionalized 1,3-butadien-2-ol esters via a new 1,3-shift of an ester moiety onto a gold-activated allene.
A. K. Buzas, F. M. Istrate, F. Gagosz, Org. Lett., 2007, 9, 985-988.
A palladium-catalyzed carbon-nitrogen bond-forming reaction of anilines and indoles with propargyl carbonates furnishes 2-amino-1,3-dienes in excellent yields under mild conditions and shows a broad functional group tolerance. The resulting 1,3-dienes are of great synthetic interest.
C. Q. O'Broin, P. J. Guiry, Org. Lett., 2020, 22, 879-883.
Highly regio- and stereoselective reactions of readily available 2-(methoxycarbonyl)-2,3-allenols with oxalyl chloride in the presence of Et3N or DMSO afforded methyl 2-(ethynyl)alk-2(E)-enoates and 2-(1′-chlorovinyl)alk-2(Z)-enoates, respectively, in good yields.
Y. Deng, X. Kin, C. Fu, S. Ma, Org. Lett., 2009, 11, 2169-2172.
Deprotonation of 3,3,3-trichloropropyl-1-triphenylphosphonium chloride generates the corresponding phosphorane, which reacts with aldehydes to give trichloromethylated (Z)-olefins, which are useful for the synthesis of (Z)-1,3-enynes, (Z,Z)-1-chloro-1,3-dienes, and 1,3-diynes in high yields and stereospecificities.
M. S. Karatholuvhu, P. L. Fuchs, J. Am. Chem. Soc., 2004, 126, 14314-14315.
Heating with NaI and DBU in dimethoxyethane effected clean elimination of tosylates to terminal olefins. This simple one-pot procedure was also applied to tosylates derived from an Evans Aldol Reaction.
P. Phukan, M. Bauer, M. E. Maier, Synthesis, 2003, 1324-1328.
In an NBS-promoted allyloxyl addition-Claisen rearrangement-dehydrobromination cascade reaction, more than 20 substituted alkynylsulfonamides were reacted with allyl alcohols to generate (2Z)-2,4-dienamides in good yields. Theoretical calculations suggested that a [3,3] sigmatropic rearrangement be the rate-limiting step.
R. Ding, Y. Li, C. Tao, B. Cheng, H. Zhai, Org. Lett., 2015, 17, 3994-3997.
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.
Palladium-catalyzed alkoxycarbonylation of 2,4-enyne carbonates proceeds in an alcohol and under balloon pressure of CO through 1,5-substitution. The olefin geometry controls the overall stereochemistry of this alkoxycarbonylation method.
E. Ş. Karagöz, M. Kuş, G. E. Akpınar, L. Artok, J. Org. Chem., 2014, 79, 9222-9230.
Pd(0)-catalyzed carbonylation of (Z)-2-en-4-yn carbonates in the presence of CO and an alcohol gives vinylallenyl esters with an exclusively E-configuration in high yields. The unreactivity of E-configured enyne carbonates may indicate that the reaction is promoted via the cooperative coordination of palladium with both alkynyl and carbonate moieties.
G. E. Akpınar, M. Kuş, M. Uçncu, E. Karakuş, L. Artok, Org. Lett., 2011, 13, 748-751.
Pd(PPh3)4-catalyzed isomerization of methylenecyclopropanes (MCPs) proceeds smoothly at 80°C in acetic acid and toluene to give 1-substituted or 1,1-disubstituted dienes in good to excellent yields. The mechanism is discussed.
M. Shi, B.-Y. Wang, J.-W. Huang, J. Org. Chem., 2005, 70, 5606-5610.
Aryl-substituted cyclopropyl carbinol derivatives undergo a facile stereoselective rearrangement catalyzed by In(OTf)3 in dichloromethane under sonication to produce the substituted conjugated all-trans-butadienes.
B. C. Ranu, S. Banerjee, Eur. J. Org. Chem., 2006, 3012-3015.
A palladium-catalyzed chemoselective protodecarboxylation of polyenoic acids provides the desired polyenes in good yields under mild conditions using either a Pd(0) or Pd(II) catalyst. The reaction tolerates a variety of aryl and aliphatic substitutions.
M. H. Al-Huniti, M. A. Perez, M. K. Garr, M. P. Croatt, Org. Lett., 2018, 20, 7375-7379.