An NMR Study of Chiral Glucopyranosyl-Based N-Heterocyclic Carbene-Palladium(II)-Pyridine Complex

doi:10.11938/cjmr20202806

Abstract

Abstract: A new air-stable and easy-to-handle 1-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-3-butyl-imidazol-2-ylidene] Pd(pyridine)Br₂ (complex 2) was synthesized from the imidazolium halide salts 1-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-3-butyl-midazolium bromide (compound 1) by reaction with Pd(OAc)₂ in pyridine. Complex 2 contains multiple chiral centers on the sugar ring. The molecular structures of complex 2 were determined with elemental analysis and liquid-state nuclear magnetic resonance (NMR) spectra. ¹H and ¹³C chemical shifts of complex 2 were fully assigned. It was found that the effects of the carbon and proton chemical environment on the sugar ring is more obvious than that on the butyl chain after formation of N-heterocyclic carbene-palladium(II)-pyridine (NHCs-Pd(II)-Py)-metal bond in the presence of multiple weakly coordinated oxygen.

Key words: liquid-state nuclear magnetic resonance, glucopyranosyl-based N-heterocyclic carbene-palladium(II)-pyridine

CLC Number:

O482.53

ZHOU Zhong-gao, XIE Qian, YUAN Yang-yang, LI Jing, LU Dong-liang, CHEN Zheng-wang. An NMR Study of Chiral Glucopyranosyl-Based N-Heterocyclic Carbene-Palladium(II)-Pyridine Complex[J]. Chinese Journal of Magnetic Resonance, 2020, 37(4): 505-514.

References

[1] BIFFIS A, CENTOMO P, DEL ZOTTO A, et al. Pd metal catalysts for cross-couplings and related reactions in the 21st century:a critical review[J]. Chem Rev, 2018, 118(4):2249-2295.
[2] DANOPOULOS A A, SIMLER T, BRAUNSTEIN P. N-heterocyclic carbene complexes of copper, nickel, and cobalt[J]. Chem Rev, 2019, 119(6):3730-3961.
[3] DODDI A, PETERS M, TAMM M. N-heterocyclic carbene adducts of main group elements and their use as ligands in transition metal chemistry[J]. Chem Rev, 2019, 119(12):6994-7112.
[4] AN Y Y, YU J G, HAN Y F. Recent advances in the chemistry of N-heterocyclic-carbene-functionalized metal-nanoparticles and their applications[J]. Chin J Chem, 2019, 37(1):76-87.
[5] MARRADI M, CHIODO F, GARCíA I, et al. Glyconanoparticles as multifunctional and multimodal carbohydrate systems[J]. Chem Soc Rev, 2013, 42(11):4728-4745.
[6] 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.
[7] NISHIOKA T, SHIBATA T, KINOSHITA I. Sugar-incorporated N-heterocyclic carbene complexes[J]. Organometallics, 2007, 26(5):1126-1128.
[8] 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.
[9] 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.
[10] TEWES F, SCHLECKER A, HARMS K, et al. Carbohydrate-containing N-heterocyclic carbene complexes[J]. J Organomet Chem, 2007, 692(21):4593-4602.
[11] SHI J C, LEI N, TONG Q S, et al. Synthesis of chiral imidazolinium carbene from a carbohydrate and its Rhodium(I) complex[J]. Eur J Inorg Chem, 2007, 2007(15):2221-2224.
[12] 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.
[13] 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.
[14] ASENSIO J M, TRICARD S, COPPEL Y, et al. Knight shift in ¹³C NMR resonances confirms the coordination of N-heterocyclic carbene ligands to water-soluble palladium nanoparticles[J]. Angew Chem Int Ed, 2016, 129(3):883-887.
[15] 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.
[16] ZHOU Z G, YUAN Y Y, HUANG L, et al. Spectral analysis of glucose-based chiral N-heterocyclic carbene precursors[J]. Chinese J Magn Reson, 2018, 35(2):215-225.周中高, 元洋洋, 黄丽, 等. 葡糖衍生手性N-杂环卡宾前体波谱学数据分析[J]. 波谱学杂志, 2018, 35(2):215-225.
[17] ZHOU Z G, QIU J, XIE L, 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.
[18] ZHOU Z G, LI M, LIU G S, et al. Ultra-small sugar-substituted N-heterocyclic carbenes protected Pd nanoparticles and catalytic activity[J]. Appl Organomet Chem, 2019, 33(7):e4942.