15614-89-8Relevant articles and documents
Frustrated Lewis Pair Polymers as Responsive Self-Healing Gels
Wang, Meng,Nudelman, Fabio,Matthes, Rebecca R.,Shaver, Michael P.
, p. 14232 - 14236 (2017)
Steric bulk prevents the formation of strong bonds between Lewis acids and bases in frustrated Lewis pairs (FLPs), where latent reactivity makes these reagents transformative in small molecule activations and metal-free catalysis. However, their use as a platform for developing materials chemistry is unexplored. Here we report a fully macromolecular FLP, built from linear copolymers that containing either a sterically encumbered Lewis base or Lewis acid as a pendant functional group. The target functional copolymers were prepared by a controlled radical copolymerization of styrene with designer boron or phosphorus containing monomers. Mixtures of the B- and P-functionalized polystyrenes do not react, with the steric bulk of the functional monomers preventing the favorable Lewis acid base interaction. Addition of a small molecule (diethyl azodicarboxylate) promotes rapid network formation, cross-linking the reactive polymer chains. The resulting gel is dynamic, can self-heal, is heat responsive, and can be reshaped by postgelation processing.
A Bond-Weakening Borinate Catalyst that Improves the Scope of the Photoredox α-C-H Alkylation of Alcohols
Kanai, Motomu,Oisaki, Kounosuke,Sakai, Kentaro
supporting information, p. 2171 - 2184 (2020/08/10)
The development of catalyst-controlled, site-selective C(sp 3)-H functionalization reactions is currently a major challenge in organic synthesis. In this paper, a novel bond-weakening catalyst that recognizes the hydroxy group of alcohols through formation of a borate is described. An electron-deficient borinic acid-ethanolamine complex enhances the chemical yield of the α-C-H alkylation of alcohols when used in conjunction with a photoredox catalyst and a hydrogen atom transfer catalyst under irradiation with visible light. This ternary hybrid catalyst system can, for example, be applied to functional-group-enriched-peptides.
Synthesis and characterization of store-operated calcium entry inhibitors active in the submicromolar range
Guilcher, Camille Le,Luyten, Tomas,Parys, Jan B.,Pucheault, Mathieu,Dellis, Olivier
, p. 1 - 23 (2021/01/01)
The store-operated calcium entry, better known as SOCE, forms the main Ca2+ influx pathway in non-excitable cells, especially in leukocytes, where it is required for cell activation and the immune response. During the past decades, several inhibitors were developed, but they lack specificity or efficacy. From the non-specific SOCE inhibitor 2-aminoethyl diphenylborinate (2-APB), we synthetized 16 new analogues by replacing/modifying the phenyl groups. Among them, our compound P11 showed the best inhibitory capacity with a Ki ≈ 75 nM. Furthermore, below 1 μM, P11 was devoid of any inhibitory activity on the two other main cellular targets of 2-APB, the IP3 receptors, and the SERCA pumps. Interestingly, Jurkat T cells secrete interleukin-2 under phytohemagglutinin stimulation but undergo cell death and stop IL-2 synthesis when stimulated in the presence of increasing P11 concentrations. Thus, P11 could represent the first member of a new and potent family of immunosuppressors.
Palladium-catalyzed cross-coupling of aryl chlorides with O, N-chelate stabilized diarylborinates
Zhang, Nan,Wang, Chen,Zou, Gang,Tang, Jie
supporting information, p. 54 - 58 (2017/05/15)
A series of O, N-chelated diarylborinates have been prepared and tested as arylboron counterpart alternative to oxygen-labile diarylborinic acids in palladium catalyzed Suzuki coupling of aryl chlorides. 3-Dimethylaminopropyl diarylborinates (B-5a), featuring a six-membered O, N-chelated boron ring that was confirmed by single crystal X-ray diffraction, displayed a delicately balanced stability and reactivity. Their cross-coupling with structurally various aryl chlorides could be effected as efficiently as that of the parent diarylborinic acids by using 0.1～1mol% Pd(OAc)2/IPr/P(OPh)3 as catalyst system, to provide the corresponding biaryls in good to excellent yields.
Synthesis of Borinic Acids and Borinate Adducts Using Diisopropylaminoborane
Marciasini, Ludovic,Cacciuttolo, Bastien,Vaultier, Michel,Pucheault, Mathieu
supporting information, p. 3532 - 3535 (2015/07/28)
In situ formation of aryl Grignard under Barbier condition and diisopropylaminoborane as boron source allows a complete control of the addition onto the boron electrophile. Analytically pure borinic acid derivatives were produced at the gram scale without column chromatography and isolated as borinates adducts, with ethanolamine or 8-hydroxyquinoline, after workup.
Design, synthesis and pharmacological characterization of analogs of 2-aminoethyl diphenylborinate (2-APB), a known store-operated calcium channel blocker, for inhibition of TRPV6-mediated calcium transport
Hofer, Alexandre,Kovacs, Gergely,Zappatini, Anna,Leuenberger, Michele,Hediger, Matthias A.,Lochner, Martin
, p. 3202 - 3213 (2013/07/11)
2-Aminoethyl diphenylborinate (2-APB) is a known modulator of the IP 3 receptor, the calcium ATPase SERCA, the calcium release-activated calcium channel Orai and TRP channels. More recently, it was shown that 2-APB is an efficient inhibitor of the epithelial calcium channel TRPV6 which is overexpressed in prostate cancer. We have conducted a structure-activity relationship study of 2-APB congeners to understand their inhibitory mode of action on TRPV6. Whereas modifying the aminoethyl moiety did not significantly change TRPV6 inhibition, substitution of the phenyl rings of 2-APB did. Our data show that the diaryl borinate moiety is required for biological activity and that the substitution pattern of the aryl rings can influence TRPV6 versus SOCE inhibition. We have also discovered that 2-APB is hydrolyzed and transesterified within minutes in solution.
Boron-catalyzed direct aldol reactions of pyruvic acids
Lee, Doris,Newman, Stephen G.,Taylor, Mark S.
supporting information; experimental part, p. 5486 - 5489 (2010/02/28)
"Chemical Equation Presented" Interactions between pyruvic acids and diphenylborinic acid form the basis of an efficient, direct, boron-catalyzed aldol reaction that takes place in water at room temperature with low catalyst loadings. Both boronic and bor
2-(N-Alkylamino)-1-(trifluoroacetimidoyl)vinyl ketone derivatives as potential reagents in heterocyclic synthesis
Vasil'Ev,Prezent,Ignatenko,Dorokhov
, p. 2359 - 2363 (2010/02/16)
A reaction of 3-acetyl-4-amino-5,5,5-trifluoropent-3-en-2-one diphenylboron chelate and ammonia or primary amines affords 4-amino-or 4-alkylamino-3- trifluoroacetimidoylpent-3-en-2-ones, new reagents which can be used for the synthesis of pyrimidines with trifluoromethyl group.
THE REACTIONS OF DIBORANE WITH ARYL-ORGANOTIN COMPOUNDS
Pickles, G. M.,Spencer, T.,Thorpe, F. G.,Chopa, A. B.,Podesta, J. C.
, p. 7 - 16 (2007/10/02)
A number of tetraaryltin compounds, Ar4Sn (where Ar = phenyl, o- and p-tolyl, and p-chlorophenyl) and tryphenyltin compounds, PH3SnX (where X = Cl, H, OH, OCOCH3 and OCOCF3) have been treated with diborane in tetrahydrofuran.Transmetallation occurs in which one or more aryl groups are transferred to boron.The organoboron intermediates give phenols upon oxidation and boronic and borinic acids upon hydrolysis.Pyridine complexes of organoboranes have also been isolated.
