3540-95-2Relevant academic research and scientific papers
Migratory Arylboration of Unactivated Alkenes Enabled by Nickel Catalysis
Wang, Wang,Ding, Chao,Li, Yangyang,Li, Zheqi,Li, Yuqiang,Peng, Long,Yin, Guoyin
supporting information, p. 4612 - 4616 (2019/03/13)
An unprecedented arylboration of unactivated terminal alkenes, featuring 1,n-regioselectivity, has been achieved by nickel catalysis. The nitrogen-based ligand plays an essential role in the success of this three-component reaction. This transformation displays good regioselectivity and excellent functional-group tolerance. In addition, the incorporation of a boron group into the products provides substantial opportunities for further transformations. Also demonstrated is that the products can be readily transformed into pharmaceutically relevant molecules. Unexpectedly, preliminary mechanistic studies indicate that although the metal migration favors the α-position of boron, selective and decisive bond formation is favored at the benzylic position.
Selective Pd-catalyzed hydrogenation of 3,3-diphenylallyl alcohol: Efficient synthesis of 3,3-diarylpropylamine drugs diisopromine and feniprane
Claudino, Thiago S.,Scholten, Jackson D.,Monteiro, Adriano L.
, p. 53 - 56 (2017/09/01)
The Pd-catalyzed selective hydrogenation of C[dbnd]C double bond in (3,3-diphenylallyl)diisopropylamine or 3,3-diphenylallyl alcohol was evaluated using different catalytic systems [Pd/C, Pd(OAc)2/ionic liquid, isolated Pd(0) nanoparticles]. For the (3,3-diphenylallyl)diisopropylamine, hydrogenolysis is preferred over hydrogenation, and only moderate selectivities were obtained for the desired product. However, complete conversion and 100% selectivity were obtained for the hydrogenation of 3,3-diphenylallyl alcohol using isolated Pd(0) nanoparticles under mild condition. This successful strategy enabled the effective synthesis of diisopromine and feniprane drugs and opens new possibilities for the preparation of other biologically active compounds.
Benzimidazolin-2-ylidene N-heterocyclic carbene complexes of ruthenium as a simple catalyst for the N-alkylation of amines using alcohols and diols
Shan, Siah Pei,Xiaoke, Xie,Gnanaprakasam, Boopathy,Dang, Tuan Thanh,Ramalingam, Balamurugan,Huynh, Han Vinh,Seayad, Abdul Majeed
, p. 4434 - 4442 (2015/02/19)
Simple air and moisture stable ruthenium complexes 1-3 and 3a were synthesized from readily available benzannulated N-heterocyclic carbene ligands (bimy = benzimidazolin-2-ylidene). These complexes were found to be efficient catalysts for the alkylation of amines using alcohols as alkylating agents. Catalysts 1, 2 and 3a gave excellent yields of up to 99% for the alkylation of various amines using benzylic and aliphatic alcohols at 130 °C for 18 h under solventless conditions. Catalyst 3a bearing both phosphine and carbene ligands gave excellent yields of up to 98% for the synthesis of heterocyclic amines by double alkylation of primary amines using linear diols. The practical utility of these catalysts was demonstrated for the synthesis of pharmaceutically important amines in a more environmentally benign way under solventless conditions.
Tandem superelectrophilic hydroarylation of CC bond and carbonyl reduction in cinnamides: Synthetic rout to 3,3-diarylpropylamines, valuable pharmaceuticals
Zakusilo, Dmitry N.,Ryabukhin, Dmitry S.,Boyarskaya, Irina A.,Yuzikhin, Oleg S.,Vasilyev, Aleksander V.
, p. 102 - 108 (2015/02/02)
Cinnamides ArCHCHCONRR′ in reactions with arenes Ar′H under the action of Bronsted (TfOH, FSO3H) or Lewis (AlBr3) superacids at rt for 1-2 h give CC bond hydroarylation products ArAr′CHCH2CONRR′ in yields of 63-98%. Reduction (LiAlH4/Et2O) of carbonyl group in the latter results in the formation of 3,3-diarylpropylamines ArAr′CHCH2CH2NRR′, valuable drugs. The reaction intermediates, superelectrophilic dications ArC+H-CH2C(OH+)NRR′, have been characterized by DFT calculations in terms of global electrophilicity index, natural charges, and atomic orbitals contributions.
Cascade synthesis of fenpiprane and related pharmaceuticals via rhodium-catalyzed hydroaminomethylation
Li, Shengkun,Huang, Kexuan,Zhang, Jiwen,Wu, Wenjun,Zhang, Xumu
supporting information, p. 1036 - 1039 (2013/04/23)
A novel rhodium catalytic system with Naphos as ligand was developed for an efficient hydroaminomethylation of 1,1-diphenylethene under relatively mild conditions. This will allow for an atom-economic and environmentally benign synthesis of fenpiprane and related pharmaceuticals.
Hydroaminomethylation with novel Rhodium-Carbene complexes: An efficient catalytic approach to pharmaceuticals
Ahmed, Moballigh,Buch, Cathleen,Routaboul, Lucie,Jackstell, Ralf,Klein, Holger,Spannenberg, Anke,Beller, Matthias
, p. 1594 - 1601 (2008/02/04)
Starting from [{Rh(cod)Cl}2] and 1,3-dimesitylimidazole-2- ylidenes the novel [RhCl(cod)(carbene)] complexes 1-5 have been synthesized, characterized, and tested in the hydroaminomethylation of aromatic olefins. The influence of different ligands and reaction parameters on the catalytic activity was investigated in detail applying 1,1-diphenylethylene and piperidine as a model system. The scope and limitations of the novel catalysts is shown in the preparation of 16 biologically active 1-amino-3,3-diarylpropenes. In general, high chemo- and regioselectivity as well as good yields of the desired products were achieved.
Dicationic electrophiles from olefinic amines in superacid
Zhang, Yun,McElrea, Aaron,Sanchez Jr., Gregorio V.,Do, Dat,Gomez, Alma,Aguirre, Sharon L.,Rendy, Rendy,Klumpp, Douglas A.
, p. 5119 - 5122 (2007/10/03)
This paper describes the superacid-catalyzed chemistry of olefinic amines and related compounds. A variety of olefinic amines are found to react with benzene in CF3SO3H (triflic acid) to give addition products in good yields (75-99%), including the pharmaceutical agents fenpiprane and prozapine. A general mechanism is proposed that invokes the formation of reactive, dicationic electrophiles and the direct observation of a diprotonated species is reported from low-temperature NMR experiments. This chemistry is also used to conveniently prepare functionalized polystyrene beads having pendant amine groups.
Hydroaminomethylation of olefins using a rhodium carbene catalyst
Seayad, Abdul Majeed,Selvakumar, Kumaravel,Ahmed, Moballigh,Beller, Matthias
, p. 1679 - 1683 (2007/10/03)
Hydroaminomethylation of terminal as well as internal aliphatic and aromatic olefins with various amines is described in the presence of [Rh(cod)(Imes)Cl] as a catalyst. In general good to excellent yields and high chemoselectivity were obtained in THF at 85-105°C using 0.1 mol% of catalyst.
Amines made easily: A highly selective hydroaminomethylation of olefins
Ahmed, Moballigh,Seayad, Abdul Majeed,Jackstell, Ralf,Beller, Matthias
, p. 10311 - 10318 (2007/10/03)
A highly chemo- and regioselective hydroaminomethylation of simple as well as functionalized α-olefins using a cationic rhodium precatalyst together with Xantphos as ligand is reported. Studies of the influence of ligands and reaction conditions led to an unprecedented selective hydroaminomethylation procedure. The novel procedure constitutes an economically attractive and environmentally favorable synthesis of secondary and tertiary aliphatic amines.
Chemistry of dicationic electrophiles: superacid-catalyzed reactions of amino acetals.
Klumpp, Douglas A,Sanchez Jr., Gregorio V,Aguirre, Sharon L,Zhang, Yun,de Leon, Sarah
, p. 5028 - 5031 (2007/10/03)
Amino acetals are shown to form highly electrophilic systems in Bronsted superacids. It is proposed that amino acetals give dicationic electrophiles, and this proposal is supported by the direct observation of a dication by low-temperature (13)C NMR. When reacted with C(6)H(6) and superacidic CF(3)SO(3)H, amino acetals are shown to provide 1-(3,3-diphenylpropyl)amines and 1-(2,2-diphenylethyl)amines as condensation products in good yields (50-99%).
