Supramolecular approaches to mediate chemical reactivity

• Pablo Ballester,
• Qi-Qiang Wang and
• Carmine Gaeta

Beilstein J. Org. Chem. 2022, 18, 1463–1465, doi:10.3762/bjoc.18.152

• catalysts were designed that showed substrate selectivity, turnover, regioselectivity, and stereoselectivity [5][6][7][8][9][10][11][12][13][14]. Supramolecular architectures with an internal cavity are potential candidates to work as supramolecular catalysts [5][6][7][8][9][10][11][12][13][14]. The first

Heteroleptic metallosupramolecular aggregates/complexation for supramolecular catalysis

• Prodip Howlader and
• Michael Schmittel

Beilstein J. Org. Chem. 2022, 18, 597–630, doi:10.3762/bjoc.18.62

• distance, now though for proximity catalysis using acyl transfer. The utility of this approach was demonstrated when a duo of catalysts was used for achieving substrate selectivity [133]. In detail, nanoswitch [Cu(130)]+ was transformed into the slow rotor [Cu2(130)]2+ (k298 = 1.34 s−1) upon the addition

Insight into functionalized-macrocycles-guided supramolecular photocatalysis

• Minzan Zuo,
• Krishnasamy Velmurugan,
• Kaiya Wang,
• Xueqi Tian and
• Xiao-Yu Hu

Beilstein J. Org. Chem. 2021, 17, 139–155, doi:10.3762/bjoc.17.15

• advantages of the macrocycles in photocatalysis including: i) substrate selectivity, ii) controllability of the rate of photochemical reactions, iii) the close proximity to substrates in a confined space, iv) the generation of a stabilized high-energy transition state, and v) macrocyclic-cavity-size

Fluorinated phenylalanines: synthesis and pharmaceutical applications

• Laila F. Awad and
• Mohammed Salah Ayoup

Beilstein J. Org. Chem. 2020, 16, 1022–1050, doi:10.3762/bjoc.16.91

• stability and substrate selectivity. 5.1. Applications of FPhe derivatives in positron emission tomography (PET) The molecular imaging technique positron emission tomography (PET) provides information on tumor metabolism, which allows for a more accurate diagnostic and therapy response in neuro-oncology

A review of asymmetric synthetic organic electrochemistry and electrocatalysis: concepts, applications, recent developments and future directions

• Munmun Ghosh,
• Valmik S. Shinde and
• Magnus Rueping

Beilstein J. Org. Chem. 2019, 15, 2710–2746, doi:10.3762/bjoc.15.264

• to the corresponding amino acid via electrochemical reduction of FAD in AOx by electron mediator ADPy. It should be noted that the authors also reported the limitation of this electrochemical method in terms of substrate selectivity of the enzymes used [44]. Electrochemical asymmetric oxidation using

Selectivity in multiple multicomponent reactions: types and synthetic applications

• Ouldouz Ghashghaei,
• Francesca Seghetti and
• Rodolfo Lavilla

Beilstein J. Org. Chem. 2019, 15, 521–534, doi:10.3762/bjoc.15.46

• helped to pave the way of combinatorial chemistry and its applications for the fast generation of pharmacological hits through library deconvolution. The reactivity of the system led to complex product mixtures, with no practical substrate selectivity. However, if in analogous experiments several

Nanoreactors for green catalysis

• M. Teresa De Martino,
• Loai K. E. A. Abdelmohsen,
• Floris P. J. T. Rutjes and
• Jan C. M. van Hest

Beilstein J. Org. Chem. 2018, 14, 716–733, doi:10.3762/bjoc.14.61

• substrates were subsequently tested using 10 mol % of this catalyst in water at room temperature. The achievement of this study was not only on the stereoselectivity of the catalysts, but also on the substrate selectivity (Table 4): the preferred substrates are water-insoluble, suggesting that the reaction

• was carried out in organic solvent [80] (Figure 4). As depicted in Table 5, substrate selectivity was observed when catalytic polymersomes were used, reasonably ascribed to a concentration effect, with more hydrophobic substrates leading to an increased local concentration around the catalyst in the

A non-canonical peptide synthetase adenylates 3-methyl-2-oxovaleric acid for auriculamide biosynthesis

• Daniel Braga,
• Dirk Hoffmeister and
• Markus Nett

Beilstein J. Org. Chem. 2016, 12, 2766–2770, doi:10.3762/bjoc.12.274

• with gramicidin synthetase from Bacillus brevis led to the identification of ten positions within an A domain (PheA), collectively referred to as nonribosomal code [14], that control substrate selectivity. Further research started to establish a relationship between this code and structural

Organic chemistry meets polymers, nanoscience, therapeutics and diagnostics

• Vincent M. Rotello

Beilstein J. Org. Chem. 2016, 12, 1638–1646, doi:10.3762/bjoc.12.161

• complex behaves differently than either of the two components. A prime example of this synergy is when we showed that nanoparticle–enzyme complexes showed altered substrate selectivity [51], with the particle dictating the enzyme kinetics by acting as a "filter" for substrate and product [47]. Another

Biosynthesis of oxygen and nitrogen-containing heterocycles in polyketides

• Franziska Hemmerling and
• Frank Hahn

Beilstein J. Org. Chem. 2016, 12, 1512–1550, doi:10.3762/bjoc.12.148

• . himastatinicus, both, glutarimides and lactones were obtained from respective substrate conversions. Thus, the domains can be seen as functionally equivalent [133]. Supported by kinetic analyses and mutational studies it was shown that B-domains, neither have an influence on the substrate selectivity nor on the

Learning from the unexpected in life and DNA self-assembly

• Jennifer M. Heemstra

Beilstein J. Org. Chem. 2015, 11, 2713–2720, doi:10.3762/bjoc.11.292

• potential to provide throughput on the order of 105–106 samples per day [18]. We envisioned that aptamers could serve as powerful recognition elements for fluorescence-based high-throughput enantiopurity measurement, and the first key element to our approach was the concept of reciprocal chiral substrate

• selectivity. According to this principle, aptamers having the same sequence, but synthesized from opposite enantiomers of DNA, will bind to opposite enantiomers of a target molecule with identical affinity and selectivity [19]. The second key element to our approach was the ability of DNA structure-switching

Dicarboxylic esters: Useful tools for the biocatalyzed synthesis of hybrid compounds and polymers

• Ivan Bassanini,
• Karl Hult and
• Sergio Riva

Beilstein J. Org. Chem. 2015, 11, 1583–1595, doi:10.3762/bjoc.11.174

• second step for polymerisation or crosslinking without the lipase. By exploiting the substrate selectivity of lipases it is possible to obtain well-defined telechelics in a one-pot, or even one-step reaction. In 1997 Uyama et al. were the first to produce telechelic polyesters from the monomers divinyl

Biosynthesis of rare hexoses using microorganisms and related enzymes

• Zijie Li,
• Yahui Gao,
• Hideki Nakanishi,
• Xiaodong Gao and
• Li Cai

Beilstein J. Org. Chem. 2013, 9, 2434–2445, doi:10.3762/bjoc.9.281

• biosynthesis and enzymatic production of rare hexoses, including ketohexoses, aldohexoses, and sugar alcohols (hexitols). To improve the production of these rare sugars, strategies for enhancing the catalytic efficiency and/or substrate selectivity of related enzymes are also discussed. Review I. Biosynthesis

Utilizing the σ-complex stability for quantifying reactivity in nucleophilic substitution of aromatic fluorides

• Magnus Liljenberg,
• Tore Brinck,
• Tobias Rein and
• Mats Svensson

Beilstein J. Org. Chem. 2013, 9, 791–799, doi:10.3762/bjoc.9.90

• structure of the σ-complex resembles the rate-limiting transition state and that this provides a rationale for the observed correlations between the SS and the reaction rate. Keywords: computational; DFT; nucleophilic aromatic substitution; reactivity; substrate selectivity; reactive intermediates