1. A Powerful Chiral Super Brønsted C-H Acid for Asymmetric Catalysis
Bingfei Peng, Jiguo Ma, Jianhua Guo, Yating Gong, Ronghao Wang, Yi Zhang, Jinlong Zeng, Wen-Wen Chen, Kuiling Ding, Baoguo Zhao J Am Chem Soc. 2022 Feb 23;144(7):2853-2860. doi: 10.1021/jacs.1c12723. Epub 2022 Feb 10.
A new type of chiral super Brønsted C-H acids, BINOL-derived phosphoryl bis((trifluoromethyl)sulfonyl) methanes (BPTMs), were developed. As compared to widely utilized BINOL-derived chiral phosphoric acids (BPAs) and N-triflyl phosphoramides (NTPAs), BPTMs displayed much higher Brønsted acidity, resulting in dramatically improved activity and excellent enantioselectivity as demonstrated in catalytic asymmetric Mukaiyama-Mannich reaction, allylic amination, three-component coupling of allyltrimethylsilane with 9-fluorenylmethyl carbamate and aldehydes, and protonation of silyl enol ether. These new strong Brønsted C-H acids have provided a platform for expanding the chemistry of asymmetric Brønsted acid catalysis.
2. A fluorescent electrophilic reagent, 9-fluorenone-4-carbonyl chloride (FCC), for the enantioresolution of amino acids on a teicoplanin phase under the elution of the methanol-based solvent mixture
T-J Hsien, S Chen Amino Acids. 2007 Jul;33(1):97-104. doi: 10.1007/s00726-006-0423-x. Epub 2006 Oct 27.
A fluorescent electrophilic reagent, 9-fluorenone-4-carbonyl chloride (FCC), is chosen to functionalize amino acids in alkaline medium before their HPLC resolution. FCC reacts with both primary and secondary amino acids to produce stable and highly fluorescent derivatives suitable for sensitive and efficient chromatographic determination and resolution on a teicoplanin chiral stationary phase (CSP) using the methanol-based solvent mixture as the mobile phase. The detection limit is in the picomole range and approximately 0.01% of the D: -enantiomer in an excess of the L: -enantiomer is detectable. However, the resolution is not reproducible under the elution of either the water- or the acetonitrile-based mobile phase. The increase in solubility of analyte in the mobile phase seems to be responsible. Upon comparison under the optimal chromatographic conditions, the resolution is better than that for the 9-fluorenylmethyl chloroformate (FMOC) or 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC) derivatives reported previously.
3. Comparison of amino acid derivatization reagents for LC-ESI-MS analysis. Introducing a novel phosphazene-based derivatization reagent
Riin Rebane, Maarja-Liisa Oldekop, Koit Herodes J Chromatogr B Analyt Technol Biomed Life Sci. 2012 Sep 1;904:99-106. doi: 10.1016/j.jchromb.2012.07.029. Epub 2012 Jul 31.
Amino acid analysis with high performance liquid chromatography with electrospray ionization mass spectrometry (LC-ESI-MS) is an emerging method. For more sensitive analysis, derivatization is used and next to commercially available derivatization reagents such as dansyl chloride (DNS), 9-fluorenylmethyl chloroformate (FMOC-Cl) and diethyl ethoxymethylenemalonate (DEEMM), new derivatization reagents are designed specially for LC-ESI-MS, like p-N,N,N-trimethylammonioanilyl N'-hydroxysuccinimidyl carbamate iodide (TAHS) which provides very low limits of detection. In this work, a novel phosphazene based derivatization reagent (FOSF) that provides comparable limits of quantitation (LoQ) to TAHS is introduced. Moreover, a thorough comparison between FOSF, TAHS, DNS, FMOC-Cl and DEEMM is carried out for 7 different amino acids - Arg, Asp, Gly, β-Ala, Pro, Trp and Phe. This is a first time that thorough comparison is carried out on the same instrument for amino acid derivatization reagents. Results on the same instrument for five amino acid derivatization reagents show that novel reagents are sensitive with LoQ values around 80 fmol but have disadvantages such as problematic chromatographic separation. Next to novel reagents, DEEMM offers very good LoQ-s (average of 150 fmol) and wide dynamic linear range.
