- Carbon Dioxide-Mediated C(sp2)-H Arylation of Primary and Secondary Benzylamines
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C-C bond formation by transition metal-catalyzed C-H activation has become an important strategy to fabricate new bonds in a rapid fashion. Despite the pharmacological importance of ortho-arylbenzylamines, however, effective ortho-C-C bond formation of free primary and secondary benzylamines using PdII remains an outstanding challenge. Presented herein is a new strategy for constructing ortho-arylated primary and secondary benzylamines mediated by carbon dioxide (CO2). The use of CO2 with Pd is critical to allowing this transformation to proceed under relatively mild conditions, and mechanistic studies indicate that it (CO2) is directly involved in the rate-determining step. Furthermore, the milder temperatures furnish free amine products that can be directly used or elaborated without the need for deprotection. In cases where diarylation is possible, an interesting chelate effect is shown to facilitate selective monoarylation.
- Kapoor, Mohit,Chand-Thakuri, Pratibha,Young, Michael C.
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supporting information
p. 7980 - 7989
(2019/05/22)
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- Rapid Ti(Oi-Pr)4 facilitated synthesis of α,α,α-trisubstituted primary amines by the addition of Grignard reagents to nitriles under microwave heating conditions
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A series of carbinamines (α,α,α-trisubstituted amines) have been prepared in a simple and efficient one-pot procedure by the addition of Grignard reagents to a series of aliphatic, aromatic and heteroaromatic nitriles. The resulting magnesium imines are subsequently converted to the desired amine after treatment with Ti(Oi-Pr)4 and additional microwave heating. Key to this procedure is the use of microwave heating for both steps of the reaction protocol, which significantly improves both reaction yields and reduces reaction times. In general, the Grignard addition reaction is complete within 5-10 min at 100 °C followed by conversion with Ti(Oi-Pr)4 and additional microwave heating to give the target amines in good yields.
- Wang, Ruifang,Gregg, Brian T.,Zhang, Wei,Golden, Kathryn C.,Quinn, John F.,Cui, Peng,Tymoshenko, Dmytro O.
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experimental part
p. 7070 - 7073
(2010/03/01)
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- One-pot synthesis of primary tert-alkylamines by the addition of organometallic reagents to nitriles mediated by Ti(Oi-Pr)4
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A number of primary tert-alkylamines (18 examples, 25-72% yields) have been prepared according to a simple one-pot procedure by the addition of organometallic reagents such as Grignard reagents and organolithium compounds to nitriles in the presence of Ti(Oi-Pr)4. Georg Thieme Verlag Stuttgart.
- Tomashenko, Olesya,Sokolov, Viktor,Tomashevskiy, Alexander,De Meijere, Armin
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p. 652 - 654
(2007/10/03)
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- Synthesis and Herbicidal Activities of 1,2-Benzisoxazole-3-acetamide Derivatives
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Many 1,2-benzisoxazole-3-acetamides were synthesized and their herbicidal activities in the paddy field were studied.Of the compounds tested, N-α,α-dimethylbenzyl-2-bromo-(1,2-benzisoxazol-3-yl)acetamide 10a was the most effective.Details of the synthesis and the results of herbicidal evaluations are given.
- Sato, Kazuo,Honma, Toyokuni,Sugai, Soji
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p. 3563 - 3568
(2007/10/02)
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