400010-14-2Relevant academic research and scientific papers
Versatile O- and S-functionalized 1,2,3-triazoliums: Ionic liquids for the Baylis-Hillman reaction and ligand precursors for stable MIC-transition metal complexes
Mendoza-Espinosa, Daniel,González-Olvera, Rodrigo,Osornio, Cecilia,Negrón-Silva, Guillermo E.,Santillan, Rosa
, p. 1587 - 1591 (2015)
The efficient synthesis of O- and S-functionalized 1,2,3-triazoliums is reported. Owing to their physical properties, these cations are efficient ionic liquids for Baylis-Hillman addition under mild reaction conditions. Simultaneously, the functionalizati
Activated Self-Resolution and Error-Correction in Catalytic Reaction Networks**
Schaufelberger, Fredrik,Ramstr?m, Olof
supporting information, p. 10335 - 10340 (2021/05/07)
Understanding the emergence of function in complex reaction networks is a primary goal of systems chemistry and origin-of-life studies. Especially challenging is to create systems that simultaneously exhibit several emergent functions that can be independently tuned. In this work, a multifunctional complex reaction network of nucleophilic small molecule catalysts for the Morita-Baylis-Hillman (MBH) reaction is demonstrated. The dynamic system exhibited triggered self-resolution, preferentially amplifying a specific catalyst/product set out of a many potential alternatives. By utilizing selective reversibility of the products of the reaction set, systemic thermodynamically driven error-correction could also be introduced. To achieve this, a dynamic covalent MBH reaction based on adducts with internal H-transfer capabilities was developed. By careful tuning of the substituents, rate accelerations of retro-MBH reactions of up to four orders of magnitude could be obtained. This study thus demonstrates how efficient self-sorting of catalytic systems can be achieved through an interplay of several complex emergent functionalities.
Unprecedented E-stereoselectivity on the sigmatropic Hurd-Claisen rearrangement of Morita-Baylis-Hillman adducts: A joint experimental-theoretical study
Silva, Vinicius Sobral,Tolentino, Terezinha Alves,Rodrigues, Tiago Costa Alves Fontoura,Santos, Fernanda Ferrari Martins,Machado, Daniel Francisco Scalabrini,Silva, Wender Alves,Oliveira, Heibbe Cristhian Benedito De,Machado, Angelo Henrique Lira
, p. 4498 - 4511 (2019/05/17)
Herein we report the first systematic investigation of the tandem mercury(ii) catalysed transvinylation/Hurd-Claisen rearrangement of MBH adducts derived from alkyl acrylates. This is the first report of E-selectivity for MBH adducts with alkyl side chain
Structure-activity relationships of GHRP-6 azapeptide ligands of the CD36 Scavenger Receptor by solid-phase submonomer azapeptide synthesis
Sabatino, David,Proulx, Caroline,Pohankova, Petra,Ong, Huy,Lubell, William D.
experimental part, p. 12493 - 12506 (2011/10/09)
The cluster of differentiation 36 (CD36) class B scavenger receptor binds a variety of biologically endogenous ligands in addition to synthetic peptides (i.e., growth hormone-releasing peptides, GHRPs), which modulate biological function related to anti-angiogenic and anti-atherosclerotic activities. Affinity labeling had previously shown that GHRP-6 analogues such as hexarelin, [2-Me-W2]GHRP-6 (1), bind to the lysine-rich domain of the CD36 receptor. Moreover, the azapeptide analogue [aza-F4]GHRP-6, 2, exhibited a characteristic β-turn conformation as described by CD and NMR spectroscopy and a slightly higher CD36 binding affinity relative to hexarelin (1.34 and 2.37 μM, respectively), suggesting receptor binding was mediated by the conformation and the aromatic residues of these peptide sequences. Ligand-receptor binding interactions were thus explored using azapeptides to examine influences of side-chain diversity and backbone conformation. In particular, considering that aromatic cation interactions may contribute to binding affinity, we have explored the potential of introducing salt bridges to furnish GHRP-6 azapeptide ligands of the CD36 receptor. Fifteen aza-glutamic acid analogues related to 2 were prepared by submonomer solid-phase synthesis. The azapeptide side chains were installed by novel approaches featuring alkylation of resin-bound semicarbazone with Michael acceptors and activated allylic acetates in the presence of phosphazene base (BTPP). Moreover, certain Michael adducts underwent intramolecular cyclization during semicarbazone deprotection, leading to novel pyrrazoline and aza-pyroglutamate N-terminal residues. Structural studies indicated that contingent on sequence the [aza-Glu]GHRP-6 analogues exhibited CD spectra characteristic of random coil, polyproline type II and β-turn secondary structures in aqueous media. In covalent competition binding studies with the GHRP-6 prototype hexarelin bearing a radiotracer, certain [aza-Glu]GHRP-6 azapeptides retained relatively high (2-27 μM) affinity for the CD36 scavenger receptor.
Baylis-Hillman reaction promoted by a recyclable protic-ionic-liquid solvent-catalyst system: DABCO-AcOH-H2O
Song, Ying,Ke, Haihua,Wang, Nan,Wang, Limin,Zou, Gang
experimental part, p. 9086 - 9090 (2010/01/16)
A recyclable protic-ionic-liquid solvent-catalyst system, DABCO-AcOH-H2O, has been developed and used in the Baylis-Hillman reaction of aromatic aldehydes, aliphatic aldehydes, and cinnamaldehydes with acrylates and acrylonitrile, showing compa
A novel ytterbium/perfluoroalkylated-pyridine catalyst for Baylis-Hillman reaction in a fluorous biphasic system
Yi, Wen-Bin,Cai, Chun,Wang, Xin
, p. 919 - 924 (2008/03/14)
Ytterbium perfluorooctanesulfonate [Yb(OPf)3] catalyses the highly efficient Baylis-Hillman reaction in the presence of a catalytic amount of a novel perfluoroalkylated-pyridine as a ligand in a fluorous biphasic system (FBS) composed of toluen
Enantioselective allylic substitution of Morita-Baylis-Hillman adducts catalyzed by planar chiral [2.2]paracyclophane monophosphines
Zhang, Tang-Zhi,Dai, Li-Xin,Hou, Xue-Long
, p. 1990 - 1994 (2008/02/13)
Planar chiral [2,2]cyclophane monophosphines are efficient catalyst in the reaction of Morita-Baylis-Hillman adducts with phthalimide. The corresponding allylic substituted products were afforded in high yields and in good to moderate ee.
The Baylis-Hillman chemistry in aqueous media: Elucidation of mechanism for synthesis of ether side-product leads to an efficient approach to C-O bond formation
Patra,Roy,Joshi,Roy,Batra,Bhaduri
, p. 663 - 670 (2007/10/03)
The formation of an ether from the Baylis-Hillman (BH) adduct during the BH reaction of 5-isoxazolecarboxaldehydes is a common phenomenon if the reaction is allowed to proceed for longer periods. The amount of formation of such ethers depends on the acryl
Rate acceleration of the Baylis-Hillman reaction in polar solvents (water and formamide). Dominant role of hydrogen bonding, not hydrophobic effects, is implicated
Aggarwal, Varinder K.,Dean, David K.,Mereu, Andrea,Williams, Richard
, p. 510 - 514 (2007/10/03)
A substantial acceleration of the Baylis-Hillman reaction between cyclohexenone and benzaldehyde has been observed when the reaction is conducted in water. Several different amine catalysts were tested, and as with reactions conducted in the absence of so
