Categories: C-C Bond Formation > Chains >
Synthesis of 1,3-dienes (dienylation)
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Recent Literature
An efficient new route by coupling Grignard reagents and dienol phosphates in
the presence of Fe(acac)3 allows a stereoselective preparation of
terminal conjugated dienes.
G. Cahiez, V. Habiak, O. Gager, Org. Lett., 2008,
10, 2389-2392.
An aerobic boron Heck reaction with cyclobutene forms exclusively
linear 1-aryl-1,3-dienes using (hetero)arylboronic acids, or 1,3,5-trienes using
alkenylboronic acids, rather than typical Heck products (i.e., substituted
cyclobutenes).
N. J. McAlpine, L. Wang, B. P. Carrow, J. Am. Chem. Soc.,
2018,
140, 13634-13639.
A highly efficient palladium-catalyzed cross-coupling reaction of
alkenyldimethyl(2-pyridyl)silanes with organic halides has been developed. The
potentially occurring two reaction pathways (carbometalation and transmetalation)
were perfectly controlled by simply changing the additives.
K. Itami, T. Nokami, J.-i. Yoshida, J. Am. Chem. Soc., 2001,
123, 5600-5601.
A regioselective base-induced ring opening of readily available sulfolenes
followed by a stereoselective palladium-catalyzed cross-coupling enable a
practical and scalable dienylation. The dienylation reaction is particularly
useful for the synthesis of synthetically challenging dienes containing cis
double bonds and conjugated polyenes.
V. T. Nguyen, H. T. Dang, H. H. Pham, V. D. Nguyen, C. Flores-Hansen, H. D.
Arman, O. V. Larionov, J. Am. Chem. Soc.,
2018,
140, 8434-8438.
A mild, stereospecific cross-coupling of unsymmetrical
1,4-bissilyl-1,3-butadienes has been developed. A selective cross-coupling
under mildly basic conditions afforded 4-aryl-1,3-dienylsilanes in excellent
yield for a wide range coupling partners. The subsequent cross-coupling of
the 4-aryl-1,3-dienylsilanes could be effected cleanly by the action of TBAF
with electron-rich or electron-poor halides.
S. E. Denmark, S. A. Tymonko, J. Am. Chem. Soc.,
2005,
127, 8004-8005.
A mild, stereospecific cross-coupling of unsymmetrical
1,4-bissilyl-1,3-butadienes has been developed. A selective cross-coupling
under mildly basic conditions afforded 4-aryl-1,3-dienylsilanes in excellent
yield for a wide range coupling partners. The subsequent cross-coupling of
the 4-aryl-1,3-dienylsilanes could be effected cleanly by the action of TBAF
with electron-rich or electron-poor halides.
S. E. Denmark, S. A. Tymonko, J. Am. Chem. Soc.,
2005,
127, 8004-8005.
A 1,4-elimination reaction of (E)-4-alkoxy-2-butenyl benzoates in the
presence of KOH and a Pd catalyst gives vinyl ethers as intermediates that can
be transformed to (2Z,4E)-2,4-pentadien-1-ols
stereoselectively via a [1,2]-Wittig rearrangement. This subsequent [1,2]-Wittg
rearrangement proceeds with retention of the stereochemistry.
T. Nakano, T. Soeta, K. Endo, K. Inomata, Y. Ukaji, J. Org. Chem., 2013,
78, 12654-12661.
The rhodium-catalyzed reaction of aryl boronic acids with internal alkynes
and acrylates in water gives the domino coupling products. The reaction
demonstrates that water offers the possibility to discover novel
transformations.
T. Kurahashi, H. Shinokubo, A. Osuka, Angew. Chem. Int. Ed., 2006,
45, 6336-6338.
Exposure of aldehydes or α-ketoesters to acetylene and hydrogen gas at
ambient temperature and pressure in the presence of a cationic rhodium catalysts
provides the products of a formal carbonyl Z-butadienylation. These
multicomponent couplings represent the first use of acetylene gas in
metal-catalyzed reductive C-C bond formation.
J. R. Kong, M. J. Krische, J. Am. Chem. Soc., 2006,
128, 16040-16041.
Catalytic hydrogenation of 1,3-enynes in the presence of ethyl glyoxalate at
ambient pressure and temperature using a rhodium catalyst modified by (R)-(3,5-tBu-4-MeOPh)-MeO-BIPHEP
results in highly regio- and enantioselective reductive coupling to furnish the
corresponding α-hydroxy esters.
Y.-T. Hong, C.-W. Cho, E. Skucas, M. J. Krische, Org. Lett., 2007,
9, 3745-3748.
Highly enantioselective direct catalytic reductive couplings of 1,3-enynes
to activated ketones such as ethyl pyruvate have been achieved by using
chirally modified cationic rhodium catalysts in the presence of hydrogen to
afford dienylated α-hydroxy esters with exceptional levels of regio- and
enantiocontrol.
J.-R. Kong, M.-Y. Ngai, M. J. Krische, J. Am. Chem. Soc.,
2006,
128, 718-719.
Hydroboration of a variety of 1-bromo-1-acetylenes with dicyclohexyl borane,
reaction with t-BuLi, and transmetalation to zinc generates a (Z)-disubstituted
vinylzinc reagent. In situ reaction of this reagent with aldehydes generates
(Z)-disubstituted allylic alcohols in high yields.
S.-J. Jeon, E. L. Fischer, P. J. Carroll, P. J. Walsh, J. Am. Chem. Soc.,
2006,
128, 9618-9619.
Pd(0) complexes can coordinate in a η2 fashion to
1,3-dienes via back-bonding to the empty antibonding molecular orbitals. The
thus more reactive, uncoordinated double bond can directly attack imines,
furnishing a formal hydrodienylation reaction. A chemoselective cascade
vinylogous addition/allylic alkylation process between 1,3-dienes and imines
with a nucleophilic group is also reported.
B.-X. Xiao, B. Jiang, R.-J. Yan, J.-X. Zhu, K. Xie, X.-Y. Gao, Q. Ouyang, W.
Du, Y.-C. Chen, J. Am. Chem. Soc.,
2021, 143, 4809-4816.
