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Synthesis of substituted alkenes

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A selective iron-catalyzed cross-coupling of primary and secondary alkyl chlorides, bromides, and iodides with alkenylzinc reagents gives the corresponding olefins in good to excellent yields in a stereospecific manner. High functional group compatibility is also demonstrated by using combinations of substrates possessing rather reactive substituents.
T. Niu, W. Zhang, D. Huang, C. Xu, H. Wang, Y. Hu, Org. Lett., 2009, 11, 4474-4477.


Highly Selective Reactions of Unbiased Alkenyl Halides and Alkylzinc Halides: Negishi-Plus Couplings
A. Krasovskiy, B. H. Lipshutz, Org. Lett., 2011, 13, 3822-3825.


The stereochemical outcome of Negishi coulings of Z-alkenyl halides is highly ligand dependent. A modified method solves the stereochemical issue and significantly improves yields of Negishi couplings in general even at ambient temperature.
A. Krasovskiy, B. H. Lipshutz, Org. Lett., 2011, 13, 3818-3821.


A nonionic amphiphile enables a simple approach to Pd-catalyzed stereoselective sp3-sp2 cross-couplings between alkyl and alkenyl bromides in the presence of zinc powder in water to give coupled products in good yields without prior formation of the organozinc reagents. The reaction is conducted at room temperature and tolerates various functional groups.
A. Krasovskiy, C. Duplais, B. H. Lipshutz, Org. Lett., 2010, 12, 4742-4744.


The use of 2% Pd2(dba)3/8% PCyp3/NMI in THF/NMP at 80°C achieves the cross-coupling of a range of β-hydrogen-containing primary alkyl iodides, bromides, chlorides, and tosylates with an array of alkyl-, alkenyl-, and arylzinc halides. This method tolerates various functional groups.
J. Zhou, G. C. Fu, J. Am. Chem. Soc., 2003, 125, 12527-12530.


An insoluble, amphiphilic and polymeric palladium catalyst (PdAS) is an excellent catalyst for the Suzuki-Miyaura reaction. The catalyst is reusable after easy work up and showed good stability in any reaction medium.
Y. M. A. Yamada, K. Takeda, H. Takashashi, S. Ikegami, J. Org. Chem., 2003, 68, 7733-7741.


"Ligandless" palladium complexes can catalyze the zirconium-Negishi reactions of alkyl electrophiles. Ligandless processes offer low cost, simplicity, and ease of purification.
S. L. Wiskur, A. Korte, G. C. Fu, J. Am. Chem. Soc., 2004, 126, 82-83.


A combination of nickel(II) acetylacetonate and (Z)-3,3-dimethyl-1,2-bis(diphenylphosphino)but-1-ene catalyzes cross-coupling reactions of alkyl aryl sulfides and alkenyl alkyl sulfides with primary and secondary alkyl Grignard reagents.
S. Kanemura, A. Kondoh, H. Yorimitsu, K. Oshima, Synthesis, 2008, 2659-2660.


In the presence of Co(PPh3)2I2, PPh3, water, and zinc powder, the reductive coupling of alkynes with alkenes having an electron-withdrawing substituent proceeded smoothly in acetonitrile to give the corresponding reductive coupling products in fair to excellent yields. Possible mechanisms for this highly regio- and stereoselective ene-yne reaction are proposed.
C.-C. Wang, P.-S. Lin, C.-H. Cheng, J. Am. Chem. Soc., 2002, 124, 9696-9697.


Use of a zirconocene catalyst based on the Brintzinger ligand and catalytic amounts of methyl aluminoxanes (MAO) effect a >99% regiocontrol of Negishi carboaluminations of 1-alkynes in toluene.
B. H. Lipshutz, T. Butler, A. Lower, J. Am. Chem. Soc., 2006, 128, 15396-15398.


The use of the Xantphos ligand in a mild palladium-catalyzed Kumada-Corriu reaction of secondary benzylic bromides with aryl and alkenyl Grignard reagents minimizes the undesired β-elimination pathway. The corresponding cross-coupling products can be isolated in good yields with inversion of the configuration.
A. López-Pérez, J. Adrio, J. C. Carretero, Org. Lett., 2009, 11, 5514-5517.


The palladium-catalyzed reaction of allyl acetates with aryl- and vinyltin reagents gave good yields of cross-coupled products. The reaction was mild and tolerant of functionality (-CO2R, -OH, -OSiR3, -OMe) in the tin reagent. Inversion of stereochemistry at the acetate center was observed, with retention of the geometry of the olefin of the allyl group and with exclusive coupling at the primary position. Retention of geometry of the olefin in the vinyltin reagents was also observed.
L. Del Valle, J. K. Stille, L. S. Hegedus, J. Org. Chem, 1990, 55, 3019-3023.


Bromoboration of propyne with BBr3 proceeds in syn-selectivity to produce (Z)-2-bromo-1-propenyldibromoborane, which is prone to stereoisomerization. Treatment with pinacol yields the stable and storable pinacolboronate. Negishi coupling gives trisubstituted (Z)-alkenylpinacolboronates in good yields. Iodinolysis of the boronates affords alkenyl iodides in good yields.
C. Wang, T. Tobrman, Z. Xu, E.-i. Negishi, Org. Lett., 2009, 11, 4092-4095.


C-O bond cleavage of lithium alkoxides occurs readily at room temperature in the presence of titanium(IV) halides. Capture of the resultant carbocation by alkynes provides an efficient route to trisubstituted (E)-alkenyl halides with high stereoselectivity.
M.-L. Yao, T. R. Quick, Z. Wu, M. P. Quinn, G. W. Kabalka, Org. Lett., 2009, 11, 2647-2649.


An easy access to (Z)-trisubstituted allylic alcohols is based on E to Z isomerization of 1-bromo-1-dialkylvinylboranes upon reaction with dialkylzinc reagents. Subsequent transmetalation to give (Z)-trisubstituted vinylzinc species is followed by trapping with aldehydes to furnish a series of (Z)-trisubstituted allylic alcohols.
Y. K. Chen, P. J. Walsh, J. Am. Chem. Soc., 2004, 126, 3702-3703.


An efficient Fe(III)-catalyzed direct coupling of alkenes with alcohols and cross-coupling of alcohols with alcohols gives the corresponding substituted (E)-alkenes stereospecifically. Mild conditions, atom efficiency, environmental soundness, and stereospecificity are features that make this procedure very attractive. Additionally, this reaction could be scaled up.
Z.-Q. Liu, Y. Zhang, L. Zhao, Z. Li, J. Wang, H. Li, L.-M. Wu, Org. Lett., 2011, 13, 2208-2211.


The use of bisphosphine ligands with a large P-Pd-P bite angle allowed to synthesize Z-chlorinated internal alkenes in good yields by a selective Suzuki-Miyaura monocoupling process of 9-alkyl-9-BBN with 1,1-dichloro-1-alkenes. These monochlorinated olefins could be further transformed providing stereospecifically trisubstituted olefins.
F. Liron, C. Fosse, A. Pernolet, E. Roulland, J. Org. Chem., 2007, 72, 2220-2223.


A catalytic asymmetric cross-coupling of α-halo carbonyl compounds with aryl metal reagents generates synthetically useful α-aryl carboxylic acid derivatives in good enantiomeric excess. The method can also be applied to enantioselective alkenylation reactions.
X. Dai, N. A. Strotman, G. C. Fu, J. Am. Chem. Soc., 2008, 130, 3302-3303.


The reaction between aryl- or vinylboroxines with α-diazocarbonyl compounds offers an alternative approach for α-arylation and α-vinylation of carbonyl compounds. α-Arylated or α-vinylated carbonyl compounds are formed under mild conditions.
C. Peng, W. Zhang, G. Yan, J. Wang, Org. Lett., 2009, 11, 1667-1670.


A radical alkenylation reaction of α-halo carbonyl compounds with styrylindium dichloride as well as unactivated alkenylindiums proceeded in the presence of triethylborane. The geometry of the carbon-carbon double bonds was retained. Efficient one-pot strategies were developed.
K. Takami, H. Yorimitsu, K. Oshima, Org. Lett., 2004, 6, 4555-4558.


An additive-free, clean conjugate addition reaction of organosiloxanes to α,β-unsaturated compounds is catalyzed by a cationic rhodium complex in dioxane/water. The mechanism involves a transmetalation step between the rhodium complex and the silicon reagent.
S. Oi, Y. Honma, Y. Inoue, Org. Lett., 2002, 4, 667-669.


C2-symmetric chiral diene ligands based on a 3,7-disubstituted bicyclo[3.3.1]nona-2,6-diene readily bind to rhodium(I). These rhodium complexes act as effective catalysts for 1,4-addition of alkenyl- and arylboronic acids to various α,β-unsaturated ketones, including several combinations that were previously difficult to provide high enantioselectivity.
R. Shintani, Y. Ichikawa, K. Takatsu, F.-X. Chen, T. Hayashi, J. Org. Chem., 2009, 74, 869-873.


Conjugate addition of dimethyl alkenylboronates to α,β-unsaturated ketones in the presence of catalytic amounts of 3,3'-disubstituted binaphthols provides alkenylation products in good yields and high enantioselectivities.
T. R. Wu, J. M. Chong, J. Am. Chem. Soc., 2007, 129, 4908-4909.


A direct conjugate addition of simple alkenes to enones has been achieved in the presence of a Ni(0)/PCy3 catalyst. This reaction is a straightforward method for the introduction of an alkenyl group at the β-position of enones.
S. Ogoshi, T. Haba, M. Ohashi, J. Am. Chem. Soc., 2009, 131, 10350-10351.


Cobalt complex/Zn systems effectively catalyze the reductive coupling of activated alkenes with alkynes in the presence of water to give substituted alkenes with very high regio- and stereoselectivity in excellent yields.
H.-T. Chang, T. T. Jayanth, C.-C. Wang, C.-H. Cheng, J. Am. Chem. Soc., 2007, 129, 12032-12041.


An efficient highly regio- and stereoselective iron-catalyzed conjugate addition of 2,3-allenoates with primary or secondary alkyl, phenyl, or vinyl Grignard reagents gives multi-substituted β,γ-unsaturated enoates in good yields. The in situ formed magnesium dienolate may readily react with different electrophilic reagents to construct an allylic quaternary carbon at the α-position of the ester group.
Z. Lu, G. Chai, S. Ma, J. Am. Chem. Soc., 2007, 129, 14546-14547.


Reductive coupling of enones or enals with alkynes using reducing agents such as organozincs, organoboranes, organosilanes, and methanol is cost-effective, and tolerant of many functional groups. Isotopic labeling strategies have provided supporting evidence for the mechanistic proposals.
W. Li, A. Herath, J. Montgomery, J. Am. Chem. Soc., 2009, 131, 17024-17029.


A nickel-catalyzed intermolecular reductive coupling of enones and alkynes gives γ,δ-unsaturated ketones. The process does not require formation of a vinyl organometallic, and a variety of functional groups including free hydroxyls and esters are tolerated.
A. Herath, B. B. Thompson, J. Montgomery, J. Am. Chem. Soc., 2007, 129, 8712-8713.


A three-component nickel-catalyzed coupling of enals, alkynes, and silanes forms an enol silane and a trisubstituted alkene with >98:2 stereoselectivity. The reaction tolerates a broad range of functionality including aldehydes, ketones, esters, free hydroxyls, and basic secondary amines.
A. Herath, J. Montgomery, J. Am. Chem. Soc., 2008, 130, 8132-8133.


A conjugate addition of organosiloxanes to α,β-unsaturated carbonyl compounds catalyzed by a cationic rhodium complex generated from [Rh(cod)(MeCN)2]BF4 and (S)-BINAP in dioxane/water gave products in good yields and excellent enantioselectivities.
S. Oi, A. Taira, Y. Honma, Y. Inoue, Org. Lett., 2003, 5, 97-99.


Treatment of 2,2-dimethylpropan-1,3-diol esters of aryl- and alkenylboronic acids with a catalytic amount of [Rh(OH)(cod)]2 in the presence of 1,3-bis(diphenylphosphino)propane and CsF in dioxane at 60°C under carbon dioxide atmosphere gave carboxylic acids in good yields.
K. Ukai, M. Aoki, J. Takaya, N. Iwasawa, J. Am. Chem. Soc., 2006, 128, 8706-8707.


An efficient iron-catalyzed cross-coupling of primary alkyl Grignard reagents allows the use of alkenyl and aryl pivalates as electrophiles under mild conditions. The combination of an inexpensive and stable carboxylate electrophile and an iron catalyst would generate ample advantages.
B.-J. Li, L. Xu, Z.-H. Wu, B.-T. Guan, C.-L. Sun, B.-Q. Wang, Z.-J. Shi, J. Am. Chem. Soc., 2009, 131, 14656-14657.


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.


Opening of the epoxide ring of enantiopure (2R,1'S)-2-(1-aminoalkyl)epoxides with different organolithium compounds gave allylamines with total selectivity and in high yields.
J. M. Concellon, J. R. Suarez, V. del Solar, Org. Lett., 2006, 8, 349-351.