- Cyclopropylboronic acid: Synthesis and Suzuki cross-coupling reactions
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An efficient synthesis of cyclopropylboronic acid is reported. This compound undergoes efficient Suzuki-type coupling reactions with a range of aryl and heteroarybromides.
- Wallace, Debra J.,Chen, Cheng-Yi
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- Palladium-catalyzed decarbonylative Suzuki-Miyaura cross-coupling of amides by carbon-nitrogen bond activation
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Palladium-catalyzed Suzuki-Miyaura cross-coupling or aryl halides is widely employed in the synthesis of many important molecules in synthetic chemistry, including pharmaceuticals, polymers and functional materials. Herein, we disclose the first palladium-catalyzed decarbonylative Suzuki-Miyaura cross-coupling of amides for the synthesis of biaryls through the selective activation of the N-C(O) bond of amides. This new method relies on the precise sequence engineering of the catalytic cycle, wherein decarbonylation occurs prior to the transmetallation step. The reaction is compatible with a wide range of boronic acids and amides, providing valuable biaryls in high yields (>60 examples). DFT studies support a mechanism involving oxidative addition, decarbonylation and transmetallation and provide insight into high N-C(O) bond activation selectivity. Most crucially, the reaction establishes the use of palladium catalysis in the biaryl Suzuki-Miyaura cross-coupling of the amide bond and should enable the design of a wide variety of cross-coupling methods in which palladium rivals the traditional biaryl synthesis from aryl halides and pseudohalides.
- Zhou, Tongliang,Ji, Chong-Lei,Hong, Xin,Szostak, Michal
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p. 9865 - 9871
(2019/11/11)
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- Facile synthesis of aryl(het)cyclopropane catalyzed by palladacycle
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Sphos (2-dicyclohexylphosphino-2′,6′-dimethoxy-1,1′- biphenyl) adduct of cyclopalladated ferrocenylimine (IIe) exhibited highly catalytic activity for the Suzuki cross-coupling reaction of cyclopropylboronic acid with aryl(het) halides with 1 mol % catalyst loading. This process was applied to both of aryl and heteroaryl halides (Br and Cl), and made the various arylcyclopropane and heteroarylcyclopropane to be easily synthesized. A variety of substituents on the aryl halides, such as alkyl, acetyl, benzoyl, ether, formyl, carboxylate, methoxy, nitro and cyano were tolerated.
- Zhang, Min,Cui, Xiuling,Chen, Xiaopei,Wang, Lianhui,Li, Jingya,Wu, Yusheng,Hou, Lifen,Wu, Yangjie
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experimental part
p. 900 - 905
(2012/02/01)
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- Palladium-catalyzed cross-coupling of cyclopropylmagnesium bromide with aryl bromides mediated by zinc halide additives
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The key Pd-catalyzed cross-coupling of aryl bromides or triflates and cyclopropylmagnesium bromide in the presence of substoichiometric amounts of zinc bromide produces cyclopropyl arenes in good to excellent yields. The cross-coupling of other alkyl, cyc
- Shu, Chutian,Sidhu, Kanwar,Zhang, Li,Wang, Xiao-Jun,Krishnamurthy, Dhileepkumar,Senanayake, Chris H.
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experimental part
p. 6677 - 6680
(2010/12/19)
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- General and user-friendly protocol for the synthesis of functionalized aryl- and heteroaryl-cyclopropanes by Negishi cross-coupling reactions
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The introduction of an unsubstituted cyclopropyl moiety was efficiently accomplished via Negishi cross-coupling of cyclopropylzinc bromide with functionalized aryl halides in high yields and fast reaction rates. The stability and the efficient one-step sy
- Coleridge, Brian M.,Bello, Charles S.,Leitner, Andreas
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experimental part
p. 4475 - 4477
(2009/12/03)
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- Cross-coupling of cyclopropyl- and cyclobutyltrifluoroborates with aryl and heteroaryl chlorides
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(Chemical Equation Presented) Suitable conditions were found for the Suzuki-Miyaura cross-coupling reaction of potassium cyclopropyl-and cyclobutyltrifluoroborates with aryl chlorides. Both of these secondary alkyl trifluoroborates coupled in moderate to excellent yield with electron-rich, electron-poor, and hindered aryl chlorides to give a variety of substituted aryl cyclopropanes and cyclobutanes.
- Molander, Gary A.,Gormisky, Paul E.
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p. 7481 - 7485
(2008/12/23)
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- Palladium-catalyzed cross-coupling reaction of tricyclopropylbismuth with aryl halides and triflates
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(Chemical Equation Presented) The palladium-catalyzed cross-coupling reaction of tricyclopropylbismuth with aryl and heterocyclic halides and triflates is reported. The reaction tolerates numerous functional groups and does not require anhydrous conditions. The method was successfully extended to the cross-coupling of triethylbismuth.
- Gagnon, Alexandre,Duplessis, Martin,Alsabeh, Pamela,Barabe, Francis
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p. 3604 - 3607
(2008/09/20)
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- Suzuki coupling of cyclopropylboronic acid with aryl halides catalyzed by a palladium-tetraphosphine complex
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The tetraphosphine all-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)- cyclopentane (Tedicyp) in combination with [Pd(C3H 5)Cl]2 affords a very efficient catalyst for the coupling of cyclopropylboronic acid with aryl bromides and aryl chlorides. Higher reactions rates were observed with aryl bromides than with aryl chlorides; however, even in the presence of 1-0.4% of catalyst, a few aryl chlorides gave the coupling products in good yields. A wide variety of substituents such as alkyl, methoxy, trifluoromethyl, acetyl, benzoyl, formyl, carboxylate, nitro, and nitrile on the aryl halides are tolerated. The coupling reaction of sterically very congested aryl bromides such as bromomesitylene or 2,4,6-triisopropylbromobenzene also proceeds in good yields. Copyright Taylor & Francis LLC.
- Lemhadri, Mhamed,Doucet, Henri,Santelli, Maurice
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p. 121 - 128
(2007/10/03)
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- The Stereochemistry of Rearrangements of Aryl and Hetaryl Groups to Primary Carbenic Centers
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The products and stereochemistries of carbenic decompositions of varied 2-aryl-1-diazoalkanes and 1-diazo-2-(2-hetaryl)propanes have been determined.
- Slack, W. E.,Taylor, W.,Moseley, C. G.,Chang, K. T.,Kraska, A.,et al.
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p. 2647 - 2650
(2007/10/02)
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- PHOTOINDUCED OXIDATIVE CLEAVAGE OF ARYLCYCLOPROPANES IN THE PRESENCE OF ORGANIC ELECTRON-ACCEPTOR
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The cyclopropane ring of arylcyclopropanes is oxidatively cleaved by irradiation in polar solvents containing nucleophiles such as alcohols, water, and sodium cyanide in the presence of electron-acceptor such as 1,4-dicyanobenzene and 1-cyanonaphthalene, giving nucleophile-incorporated products.This photoreaction proceeds via an electron-transfer from the cyclopropanes to the excited electron-acceptors, and the cation radicals of arylcyclopropanes are involved as key intermediates.
- Mizuno, Kazuhiko,Ogawa, Jun,Otsuji, Yoshio
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p. 741 - 744
(2007/10/02)
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