67205-88-3Relevant academic research and scientific papers
Diarylmethane compounds as well as preparation method and application thereof
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Paragraph 0139; 0143-0148; 0179-0184, (2019/08/20)
The invention discloses diarylmethane compounds as well as a preparation method and application thereof. The diarylmethane compounds have a molecular structural general formula as defined by a generalformula (I) in the description. The preparation method of the diarylmethane compounds comprises the steps of adding a benzyl halogenated hydrocarbon compound A and an arylboronic acid B into a reaction system containing an organic small-molecular catalyst, an alkali reagent and a solvent, and performing a reaction to prepare the compounds. The diarylmethane compounds provided by the invention contain electron withdrawing groups and an electron-donating group substituted diarylmethane basic structure, and can be widely used for synthesis of pharmaceutical intermediates, particularly polysubstituted methane compounds, and preparation of functional materials; and the preparation method has a simple process and low requirements for reaction conditions, the reaction process is safe and controllable, the atomic utilization rate and production efficiency are high, the regioselectivity and stereoselectivity of the products are efficiently ensured, a frontier science small-molecule organocatalysis concept is introduced, and the method is friendly to the environment.
Transition-Metal-Free Suzuki-Type Cross-Coupling Reaction of Benzyl Halides and Boronic Acids via 1,2-Metalate Shift
He, Zhiqi,Song, Feifei,Sun, Huan,Huang, Yong
supporting information, p. 2693 - 2699 (2018/02/28)
Cross-coupling of organoboron compounds with electrophiles (Suzuki-Miyaura reaction) has greatly advanced C-C bond formation and has been well received in medicinal chemistry. During the past 50 years, transition metals have played a central role throughout the catalytic cycle of this important transformation. In this process, chemoselectivity among multiple carbon-halogen bonds is a common challenge. In particular, selective oxidative addition of transition metals to alkyl halides rather than aryl halides is difficult due to unfavorable transition states and bond strengths. We describe a new approach that uses a single organic sulfide catalyst to activate both C(sp3) halides and arylboronic acids via a zwitterionic boron "ate" intermediate. This "ate" species undergoes a 1,2-metalate shift to afford Suzuki coupling products using benzyl chlorides and arylboronic acids. Various diaryl methane analogues can be prepared, including those with complex and biologically active motifs. The reactions proceed under transition-metal-free conditions, and C(sp2) halides, including aryl bromides and iodides, are unaffected. The orthogonal chemoselectivity is demonstrated in the streamlined synthesis of highly functionalized diaryl methane scaffolds using multi-halogenated substrates. Preliminary mechanistic experiments suggest both the sulfonium salt and the sulfur ylide are involved in the reaction, with the formation of sulfonium salt being the slowest step in the overall catalytic cycle.
Cobalt-Catalyzed Reductive Cross-Coupling Between Benzyl Chlorides and Aryl Halides
Pal, Suman,Chowdhury, Sushobhan,Rozwadowski, Elodie,Auffrant, Audrey,Gosmini, Corinne
supporting information, p. 2431 - 2435 (2016/08/16)
A new protocol for the direct reductive cobalt-catalyzed arylation of benzyl chlorides has been developed in order to form functionalized diarylmethanes. A variety of reactive groups either on the aryl or the benzyl halide was employed. This represents the first cobalt-catalyzed reductive cross-coupling which does not require any ligand and pyridine. A reaction pathway is proposed involving a radical benzyl species. (Figure presented.).
A practical cobalt-catalyzed cross-coupling of benzylic zinc reagents with aryl and heteroaryl bromides or chlorides
Benischke, Andreas D.,Knoll, Irina,Rérat, Alice,Gosmini, Corinne,Knochel, Paul
supporting information, p. 3171 - 3174 (2016/02/20)
A catalytic system consisting of 5 mol% CoCl2 and 10 mol% isoquinoline allows a convenient cross-coupling of benzylic zinc reagents with various aryl and heteroaryl bromides or chlorides leading to polyfunctionalized diaryl- and aryl-heteroaryl-methane derivatives.
New preparation of benzylic manganese chlorides by the direct insertion of magnesium into benzylic chlorides in the presence of MnCl2·2LiCl
Quinio, Pauline,Benischke, Andreas D.,Moyeux, Alban,Cahiez, Gérard,Knochel, Paul
supporting information, p. 514 - 518 (2015/04/14)
Functionalized benzylic manganese chlorides were smoothly prepared by the direct insertion of magnesium into benzylic chlorides in the presence of MnCl2·2LiCl. Reactions with acid chlorides, aldehydes, an allyl bromide, and an enone proceed without any additional transition metal.
Pd-catalyzed chemoselective threefold cross-coupling of triarylbismuths with benzylic bromides
Rao, Maddali L. N.,Dhanorkar, Ritesh J.
, p. 6794 - 6798 (2013/05/23)
An efficient palladium-catalyzed protocol was demonstrated for the chemoselective cross-coupling of functionalized benzylic bromides with triarylbismuth reagents. Under the established conditions, catalyzed by palladium in the presence of K3PO
Direct Pd-catalyzed cross-coupling of functionalized organoaluminum reagents
Groll, Klaus,Bluemke, Tobias D.,Unsinn, Andreas,Haas, Diana,Knochel, Paul
supporting information, p. 11157 - 11161,5 (2012/12/12)
A handsome couple: Through the use of the simple Pd catalyst [Pd(tmpp) 2Cl2] (tmpp=tris(2,4,6-trimethoxyphenyl)phosphine) and THF/DMF as solvent, various aryl-, heteroaryl-, benzyl- and alkylaluminum reagents can be readily cross-coupled with aryl or heteroaryl iodides, bromides, and nonaflates, and in special cases even with chlorides and triflates. This cross-coupling tolerates free NH2 groups, aldehydes, ketones, esters, and nitro functions. Copyright
One-pot synthesis of symmetrical and unsymmetrical diarylmethanes via diborylmethane
Endo, Kohei,Ishioka, Takafumi,Ohkubo, Takahiro,Shibata, Takanori
, p. 7223 - 7231 (2012/10/29)
A one-pot synthesis of diarylmethanes from air-stable diborylmethane via the Suzuki-Miyaura cross-coupling reaction is described. The present approach realizes the synthesis of various symmetrical and unsymmetrical diarylmethanes in good to excellent yields.
Direct method for carbon-carbon bond formation: The functional group tolerant cobalt-catalyzed alkylation of aryl halides
Amatore, Muriel,Gosmini, Corinne
supporting information; experimental part, p. 5848 - 5852 (2010/09/03)
(Figure Presented). A new protocol for the direct cobaltcatalyzed alkylation of aryl halides has been developed that proceeds smoothly in the presence of phosphanes or bipyridines as ligands with a variety of alkyl halides, including challenging alkyl electrophiles bearing β hydrogen atoms (see scheme). Sensitive functional groups are tolerated on both coupling partners, thus, significantly extending the general scope of transition-metal-catalyzed alkylation of aryl halides.
LiCl-mediated preparation of functionalized benzylic indium(III) halides and highly chemoselective palladium-catalyzed cross-coupling in a protic cosolvent
Chen, Yi-Hung,Sun, Mai,Knochel, Paul
supporting information; experimental part, p. 2236 - 2239 (2009/08/14)
(Chemical Equation Presented) Sensitive functional groups such as COR, CHO, or CH2OH can be present in benzylic indium reagents prepared by the direct insertion of indium in the presence of LiCl. These reagents undergo palladium-catalyzed cross
