Spectral Analysis of Glucose-Based Chiral N-heterocyclic Carbene Precursors

doi:10.11938/cjmr20172595

Abstract

Abstract: 1-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-3-butylimidazolium bromide (compound 2) was synthesized with 1-bromobutane and 1-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl) imidazole (compound 1), which is a glucose-derived chiral N-heterocyclic carbene precursor. Multiple chiral carbon atoms in compound 2 lead to quite complex nuclear magnetic resonance (NMR) spectra. In this study, we analyzed compound 2 using elemental analysis, infrared absorption spectroscopy (IR), liquid chromatography-high resolution mass spectrometry (LC-HRMS), and assigned the ¹H NMR and 13C NMR signals with one-dimensional (1D) and two-dimensional (2D) NMR spectroscopy, including ¹H NMR, 13C NMR, DEPT135, DEPT90, DEPT45, COSY, ¹H-¹³C HSQC and ¹H-¹³C HMBC.

Key words: liquid NMR, chiral N-heterocyclic carbene precursor, glucose, spectral analysis

CLC Number:

O482.53

ZHOU Zhong-gao, YUAN Yang-yang, HUANG Li, LIU Jin-xiang, XIE Yong-rong. Spectral Analysis of Glucose-Based Chiral N-heterocyclic Carbene Precursors[J]. Chinese Journal of Magnetic Resonance, 2018, 35(2): 215-225.

References

[1] KAPDI A R, FAIRLAMB I J. Anti-cancer palladium complexes:a focus on PdX₂L₂, palladacycles and related complexes[J]. Chem Soc Rev, 2014, 43(13):4751-4777.
[2] DÍEZ-GONZÁLEZ S, MARION N, NOLAN S P. N-Heterocyclic carbenes in late transition metal catalysis[J]. Chem Rev, 2009, 109(8):3612-3676.
[3] HINDI K M, PANZNER M J, TESSIER C A, et al. The medicinal applications of imidazolium carbene-metal complex es[J]. Chem Rev, 2009, 109(8):3859-3884.
[4] SHAW C F. Gold-based therapeutic agents[J]. Chem Rev, 1999, 99(9):2589-2600.
[5] VELAZQUEZ H D, VERPOORT F. N-heterocyclic carbene transition metal complexes for catalysis in aqueous media[J]. Chem Soc Rev, 2012, 41(21):7032-7060.
[6] HOPKINSON M N, RICHTER C, SCHEDLER M, et al. An overview of N-heterocyclic carbenes[J]. Nature, 2014, 510(7506):485-496.
[7] GYURCSIK B, NAGY L. Carbohydrates as ligands:coordination equilibria and structure of the metal complexes[J]. Coord Ch em Rev, 2000, 203(1):81-149.
[8] ZHAO W, FERRO V, BAKER M V. Carbohydrate-N-heterocyclic carbene metal complexes:synthesis, catalysis and biological studies[J]. Coord Chem Rev, 2017, 339:1-16.
[9] IMANAKA Y, HASHIMOTO H, KINOSHITA I, et al. Incorporation of a sugar unit into a C-C-N pincer Pd complex using click chemistry and Its dynamic behavior in solution and catalytic ability toward the Suzuki-Miyaura coupling in water[J]. Chem Lett, 2014, 43(5):687-689.
[10] NISHIOKA T, SHIBATA T, KINOSHITA I. Sugar-incorporated N-heterocyclic carbene complexes[J]. Organometallics, 2007, 26(5):1126-1128.
[11] HENDERSON A S, BOWER J F, GALAN M C. Carbohydrate-based N-heterocyclic carbenes for enantioselective catalysis[J]. Org Biomol Chem, 2014, 12(45):9180-9183.
[12] HENDERSON A S, BOWER J F, GALAN M C. Carbohydrates as enantioinduction components in stereoselective catalysis[J]. Org Biomol Chem, 2016, 14(17):4008-4017.
[13] TEWES F, SCHLECKER A, HARMS K, et al. Carbohydrate-containing N-heterocyclic carbene complexes[J]. J Organomet Chem., 2007, 692(21):4593-4602.
[14] SHI J C, LEI N, TONG Q, et al. Synthesis of chiral imidazolinium carbene from a carbohydrate and its Rhodium(I) complex[J]. E ur J Inorg Chem, 2007, 2007(15):2221-2224.
[15] SHIBATA T, ITO S, DOE M, et al. Dynamic behaviour attributed to chiral carbohydrate substituents of N-heterocyclic carbene ligands in square planar nickel complexes[J]. Dalton Trans, 2011, 40(25):6778-6784.
[16] ZHOU Z G, LIU P, TONG Q S, et al. NMR studies on methyl 4, 6-O-benzyl idene-3-deoxy-3-(salicylideneamino)-α-D-altropyranoside[J]. Journal of Fujian Normal University, 2009, 5:78-80. 周中高, 刘沛, 童庆松, 等. 甲基3-脱氧-3-(2-羟基苄叉氨基)-4, 6-O-苄叉基-α-D-阿卓吡喃糖苷的NMR研究[J]. 福建师范大学学报, 2009, 5:78-80.
[17] YANG Z C, ZHOU H H, ZHOU Z Y, et al. Synthesis and characterization of 1-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)imidazole[J]. Chenmical Intermediate, 2013, 2:22-26. 杨志才, 周海红, 周珍云, 等. 手性NHC中间体1-(2, 3, 4, 6-四-O-乙酰基-β-D-吡喃葡萄糖基)咪唑的合成及核磁共振研究[J]. 化工中间体, 2013, 2:22-26.
[18] ZHOU Z G, ZHAO Y, ZHEN H Y, et al. Poly(ethylene glycol)-and glucopyranoside-substituted N-heterocyclic carbene precursors for the synthesis of arylfluorene derivatives using efficient palladium-catalyzed aqueous Suzuki reaction[J]. Appl Organomet Chem, 2016, 30(11):924-931.
[19] ZHOU Z G, QIU J B, XIE L F, et al. Synthesis of chiral imidazolium salts from a carbohydrate and their application in Pd-catalyzed Suzuki-Miyaura reaction[J]. Catal Lett, 2014, 144(11):1911-1918.
[20] YU D H, KANG W, HAO F, et al. Spectroscopic studies and structural elucidation of cabazitaxel[J]. Chinese J Magn Reson, 2017, 34(2):191-199. 余大海, 康旺, 郝福, 等. 卡巴他赛结构确证的波谱学研究[J]. 波谱学杂志, 2017, 34(2):191-199.
[21] ZHANG E, CUI D Y, SUN W, et al. Structural elucidation of a hydrolysis product from derivatives of allofuranose[J]. Chinese J Magn Reson, 2017, 34(2):183-190. 张恩, 崔得运, 孙伟, 等. 呋喃阿洛糖衍生物水解产物的结构确定[J]. 波谱学杂志, 2017, 34(2):183-190.