Organic Letters
Letter
́
́
(g) Franzoni, I.; Guenee, L.; Mazet, C. Access to congested
quaternary centers by Pd-catalyzed intermolecular γ-arylation of
unactivated α,β-unsaturated aldehydes. Chem. Sci. 2013, 4 (6), 2619−
2624. (h) Wu, H.; Radomkit, S.; O’Brien, J. M.; Hoveyda, A. H.
Metal-free catalytic enantioselective C-B bond formation: (pinacola-
to)boron conjugate additions to alpha,beta-unsaturated ketones,
esters, Weinreb amides, and aldehydes promoted by chiral N-
heterocyclic carbenes. J. Am. Chem. Soc. 2012, 134 (19), 8277−8285.
(i) Fernandez, M.; Uria, U.; Vicario, J. L.; Reyes, E.; Carrillo, L.
Enantioselective conjugate addition of donor-acceptor hydrazones to
alpha,beta-unsaturated aldehydes through formal diaza-ene reaction:
access to 1,4-dicarbonyl compounds. J. Am. Chem. Soc. 2012, 134
(29), 11872−11875. (j) Momiyama, N.; Konno, T.; Furiya, Y.;
Iwamoto, T.; Terada, M. Design of chiral bis-phosphoric acid catalyst
derived from (R)-3,3′-di(2-hydroxy-3-arylphenyl)binaphthol: cata-
lytic enantioselective Diels-Alder reaction of alpha,beta-unsaturated
aldehydes with amidodienes. J. Am. Chem. Soc. 2011, 133 (48),
19294−19297. (k) Hashimoto, T.; Maeda, Y.; Omote, M.; Nakatsu,
H.; Maruoka, K. Catalytic enantioselective 1, 3-dipolar cycloaddition
of C, N-cyclic azomethine imines with α, β-unsaturated aldehydes. J.
Am. Chem. Soc. 2010, 132 (12), 4076−4077. (l) De Sarkar, S.; Studer,
A. NHC-catalyzed Michael addition to alpha,beta-unsaturated
aldehydes by redox activation. Angew. Chem., Int. Ed. 2010, 49
(48), 9266−9. (m) Chiang, P.-C.; Rommel, M.; Bode, J. W. α′-
hydroxyenones as mechanistic probes and scope-expanding surrogates
for α, β-Unsaturated aldehydes in N-heterocyclic carbene-catalyzed
reactions. J. Am. Chem. Soc. 2009, 131 (24), 8714−8718.
dihydroxylation and trans-aminohydroxylation of α, β-unsaturated
aldehydes via an organocatalytic reaction cascade. J. Am. Chem. Soc.
2010, 132 (26), 9188−9196. (b) Nielsen, M.; Jacobsen, C. B.; Paixao,
M. W.; Holub, N.; Jørgensen, K. A. Asymmetric organocatalytic
formal alkynylation and alkenylation of α, β-unsaturated aldehydes. J.
Am. Chem. Soc. 2009, 131 (30), 10581−10586.
(4) Meazza, M.; Tur, F.; Hammer, N.; Jorgensen, K. A. Synergistic
Diastereo- and Enantioselective Functionalization of Unactivated
Alkyl Quinolines with alpha,beta-Unsaturated Aldehydes. Angew.
Chem., Int. Ed. 2017, 56 (6), 1634−1638.
(5) (a) Liu, H.; Mei, Q.; Li, S.; Yang, Y.; Wang, Y.; Liu, H.; Zheng,
L.; An, P.; Zhang, J.; Han, B. Selective hydrogenation of unsaturated
aldehydes over Pt nanoparticles promoted by the cooperation of steric
and electronic effects. Chem. Commun. 2018, 54 (8), 908−911.
(b) Kutwal, M. S.; Appayee, C. Highly Regio- and Enantioselective γ-
Alkylation of Linear α,β-Unsaturated Aldehydes. Eur. J. Org. Chem.
2017, 2017 (29), 4230−4234. (c) Luo, C.-W.; Chao, Z.-S.
Unsaturated aldehydes: a novel route for the synthesis of pyridine
and 3-picoline. RSC Adv. 2015, 5 (67), 54090−54101. (d) Buffa, R.;
Sedova, P.; Basarabova, I.; Moravcova, M.; Wolfova, L.; Bobula, T.;
Velebny, V. alpha,beta-Unsaturated aldehyde of hyaluronan–Syn-
thesis, analysis and applications. Carbohydr. Polym. 2015, 134, 293−
299. (e) Shi, Z.; Grohmann, C.; Glorius, F. Mild rhodium(III)-
catalyzed cyclization of amides with alpha,beta-unsaturated aldehydes
and ketones to azepinones: application to the synthesis of the
homoprotoberberine framework. Angew. Chem., Int. Ed. 2013, 52
(20), 5393−8397. (f) Reddy, L. V.; Kumar, V.; Sagar, R.; Shaw, A. K.
Glycal-derived delta-hydroxy alpha,beta-unsaturated aldehydes (Perlin
aldehydes): versatile building blocks in organic synthesis. Chem. Rev.
2013, 113 (5), 3605−3631. (g) Ibrahem, I.; Ma, G.; Afewerki, S.;
Cordova, A. Palladium/chiral amine co-catalyzed enantioselective
beta-arylation of alpha,beta-unsaturated aldehydes. Angew. Chem., Int.
Ed. 2013, 52 (3), 878−82.
(6) Hu, B.; Liu, T. X.; Zhang, P.; Liu, Q.; Bi, J.; Shi, L.; Zhang, Z.;
Zhang, G. N-Heterocyclic Carbene-Catalyzed alpha,beta-Unsaturated
Aldehydes Umpolung in Fullerene Chemistry: Construction of
[60]Fullerene-Fused Cyclopentan-1-ones and Cyclohex-2-en-1-ones.
Org. Lett. 2018, 20 (16), 4801−4805.
(7) (a) Zhu, M.; Huang, B.; Shao, Q.; Pi, Y.; Qian, Y.; Huang, X.
Highly Networked Platinum-Tin Nanowires as Highly Active and
Selective Catalysts towards the Semihydrogenation of Unsaturated
Aldehydes. ChemCatChem 2018, 10 (15), 3214−3218. (b) Breuer,
M.; Ditrich, K.; Habicher, T.; Hauer, B.; Kesseler, M.; Sturmer, R.;
Zelinski, T. Industrial methods for the production of optically active
intermediates. Angew. Chem., Int. Ed. 2004, 43 (7), 788−824.
(8) Ma, Z.; Wang, Y. Dirhodium(ii)/P(t-Bu)3 catalyzed tandem
reaction of alpha,beta-unsaturated aldehydes with arylboronic acids.
Org. Biomol. Chem. 2018, 16 (40), 7470−7476.
(9) Wang, G.; Xu, Y.; Zhang, S.; Li, Z.; Li, C. An ionic liquid
catalyzed probase method for one-pot synthesis of α,β-unsaturated
esters from esters and aldehydes under mild conditions. Green Chem.
2017, 19 (20), 4838−4848.
(10) (a) Bauer, K.; Garbe, D.; Surburg, H. In Common Fragrance and
Flavor Materials; Wiley-VCH: Weinheim, 2001; pp 11−39. (b) Sell,
C., Ed. In The Chemistry of Fragrances: From Perfumer to Consumer;
The Royal Society of Chemistry: Cambridge, 2006; pp 54−95.
(11) Tojo, G.; FernPndes, M. In Oxidation of Alcohols to Aldehydes
and Ketones: A Guide to Current Common Practice; Tojo, G., Ed.;
Springer: Berlin, 2006; pp 1−375.
(2) (a) Qiu, Y.; Dlugosch, M.; Liu, X.; Khan, F.; Ward, J. S.; Lan, P.;
Banwell, M. G. Reductive Cyclization of o-Nitroarylated-alpha,beta-
unsaturated Aldehydes and Ketones with TiCl3/HCl or Fe/HCl
Leading to 1,2,3,9-Tetrahydro-4 H-carbazol-4-ones and Related
Heterocycles. J. Org. Chem. 2018, 83 (19), 12023−12033.
(b) Yang, P.; Wang, X.; Chen, F.; Zhang, Z. B.; Chen, C.; Peng, L.;
Wang, L. X. Organocatalytic Enantioselective Michael/Cyclization
Domino Reaction between 3-Amideoxindoles and alpha,beta-Unsa-
turated Aldehydes: One-Pot Preparation of Chiral Spirocyclic
Oxindole-gamma-lactams. J. Org. Chem. 2017, 82 (7), 3908−3916.
(c) Selva, V.; Larranaga, O.; Castello, L. M.; Najera, C.; Sansano, J.
M.; de Cozar, A. Diastereoselective [3 + 2] vs [4 + 2] Cycloadditions
of Nitroprolinates with alpha,beta-Unsaturated Aldehydes and
Electrophilic Alkenes: An Example of Total Periselectivity. J. Org.
Chem. 2017, 82 (12), 6298−6312. (d) Hu, L.; Lu, X.; Deng, L.
Catalytic Enantioselective Peroxidation of alpha,beta-Unsaturated
Aldehydes for the Asymmetric Synthesis of Biologically Important
Chiral Endoperoxides. J. Am. Chem. Soc. 2015, 137 (26), 8400−8403.
(e) Schroeder, M.; Mathys, M.; Ehrensperger, N.; Buchel, M. γ-
̈
Unsaturated Aldehydes as Potential Lilial Replacers. Chem. Biodiver-
sity 2014, 11 (10), 1651−1673. (f) Jin, X.; Yamaguchi, K.; Mizuno, N.
Gold-catalyzed heterogeneous aerobic dehydrogenative amination of
alpha,beta-unsaturated aldehydes to enaminals. Angew. Chem., Int. Ed.
2014, 53 (2), 455−458. (g) Akagawa, K.; Kudo, K. Construction of
an all-carbon quaternary stereocenter by the peptide-catalyzed
asymmetric Michael addition of nitromethane to beta-disubstituted
alpha,beta-unsaturated aldehydes. Angew. Chem., Int. Ed. 2012, 51
(51), 12786−12789. (h) Hubner, S.; Jiao, H.; Michalik, D.;
Neumann, H.; Klaus, S.; Strubing, D.; Spannenberg, A.; Beller, M.
In situ generation of chiral N-dienyl lactams in a multicomponent
reaction: an efficient and highly selective way to asymmetric
amidocyclohexenes. Chem. - Asian J. 2007, 2 (6), 720−733. (i) Jacobi
von Wangelin, A.; Neumann, H.; Gordes, D.; Klaus, S.; Strubing, D.;
Beller, M. Multicomponent coupling reactions for organic synthesis:
chemoselective reactions with amide-aldehyde mixtures. Chem. - Eur.
J. 2003, 9 (18), 4286−4294. (j) Neumann, H.; Jacobi von Wangelin,
(12) Maryanoff, B. E.; Reitz, A. B. The Wittig olefination reaction
and modifications involving phosphoryl-stabilized carbanions. Stereo-
chemistry, mechanism, and selected synthetic aspects. Chem. Rev.
1989, 89 (4), 863−927.
(13) Ager, D. J. The Peterson Reaction. Synthesis 1984, 1984 (05),
384−398.
(14) Fang, X.; Jackstell, R.; Franke, R.; Beller, M. Domino-
hydroformylation/aldol condensation catalysis: highly selective syn-
thesis of alpha,beta-unsaturated aldehydes from olefins. Chem. - Eur. J.
2014, 20 (41), 13210−13216.
̈
A.; Gordes, D.; Spannenberg, A.; Beller, M. A New Multicomponent
Coupling of Aldehydes, Amides, and Dienophiles: Atom-Efficient
One-Pot Synthesis of Highly Substituted Cyclohexenes and Cyclo-
hexadienes. J. Am. Chem. Soc. 2001, 123 (34), 8398−8399.
(3) (a) Albrecht, Ł.; Jiang, H.; Dickmeiss, G.; Gschwend, B. r.;
Hansen, S. G.; Jørgensen, K. A. Asymmetric formal trans-
D
Org. Lett. XXXX, XXX, XXX−XXX