Page 220 - 《精细化工》2022年第7期

·1506· 精细化工 FINE CHEMICALS 第 39 卷

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碳自由基 A。随后，荧光素自由基离子（FI ）在 TBHP heterocycles[J]. Chemical Reviews, 2008, 108(8): 3395-3442.
的氧化作用下回到基态，同时释放出叔丁氧自由基 [3] GUO X X, GU D W, WU Z, et al. Copper-catalyzed C—H
functionalization reactions: Efficient synthesis of heterocycles[J].
（t-BuO•）和氢氧负离子。碳自由基 A 进一步对 N- Chemical Reviews, 2015, 115(3): 1622-1651.
苯并咪唑基丙烯酰胺类化合物中不饱和双键发生自 [4] WU B, YOSHIKAI N. Recent developments in synthetic methods
for benzo[b]heteroles[J]. Organic & Biomolecular Chemistry, 2016,
由基加成反应生成中间体 B，进一步环化得到自由基
14(24): 5402-5416.
中间体 C。中间体 C 在叔丁氧自由基作用下脱去叔 [5] PAN F, SHU C, YE L W. Recent progress towards gold-catalyzed
丁醇生成最终产物（Path 1），或者进一步被氧化成 synthesis of N-containing tricyclic compounds based on ynamides
[J]. Organic & Biomolecular Chemistry, 2016, 14(40): 9456-9465.
碳正离子中间体 D 后在氢氧负离子作用下脱去水分 [6] XIE W, WU Y, ZHANG J, et al. Design, synthesis and biological
子得到终产物（Path 2）。 evaluations of novel pyridone-thiazole hybrid molecules as antitumor
agents[J]. European Journal of Medicinal Chemistry, 2018, 145(1): 35-40.
[7] ALAM K, HONG S W, OH K H, et al. Divergent C—H annulation
for multifused N-heterocycles: Regio- and stereospecific cyclizations
of N-alkynylindoles[J]. Angewandte Chemie International Edition,
2017, 56(43): 13387-13391.
[8] TAUBLAENDER M J, GLKLHOFERl F M, UNTERLASS M M.
Green and rapid hydrothermal crystallization and synthesis of fully
conjugated aromatic compounds[J]. Angewandte Chemie International
Edition, 2018, 57(38): 12270-12274.
[9] MENG G, NIU H Y, QU G R, et al. Synthesis of fused N-heterocycles
via tandem C—H activation[J]. Chemical Communications, 2012,
48(77): 9601-9603.
[10] PEREIRA K C, PORTER A L, DEBOEF B. Intramolecular arylation
of benzimidazoles via Pd(Ⅱ)/Cu(Ⅰ) catalyzed cross-dehydrogenative
coupling[J]. Tetrahedron Letters, 2014, 55(10): 1729-1732.
[11] LI C J. Cross-dehydrogenative coupling (CDC): Exploring C—C bond

formations beyond functional group transformations[J]. Accounts of
Chemical Research, 2009, 42(2): 335-344.
图 1 可能的反应机理 [12] YEUNG C S, DONG V M. Catalytic dehydrogenative cross-coupling:
Fig. 1 Possible reaction mechanism Forming carbon-carbon bonds by oxidizing two carbon-hydrogen

bonds[J]. Chemical Reviews, 2011, 111(3): 1215-1292.
[13] GIRARD S A, KNAUBER T, LI C J. The cross-dehydrogenative
3 结论 coupling of C—H bonds: A versatile strategy for C—C bond formations
[J]. Angewandte Chemie International Edition, 2014, 53(1): 74-100.
报道了可见光促进下荧光素催化的 N-苯并咪唑 [14] LIU C, YUAN J, GAO M, et al. Oxidative coupling between two
基丙烯酰胺类化合物与 1,3-二氧戊烷的氧化偶联反应 hydrocarbons: An update of recent C—H functionalizations[J]. Chemical
Reviews, 2015, 115(22): 12138-12204.
构建苯并咪唑[2,1-a]异喹啉-6(5H)-酮衍生物的方 [15] VERENDEL J J, NORDLUND M, ANDERSSON P G. Selective
法。得到最优反应条件：N-苯并咪唑基丙烯酰胺类 metal-catalyzed transfer of H 2 and CO from polyols to alkenes[J].
ChemSusChem, 2013, 6(3): 426-429.
化合物（0.25 mmol）、催化剂荧光素（0.0125 mmol）、
[16] CHRISTENSEN S H, OLSEN E P, ROSENBAUM J. Hydroformylation
1,3-二氧戊烷 2 mL、TBHP 氧化剂（0.75 mmol），室 of olefins and reductive carbonylation of aryl halides with syngas
温蓝光（LED，10 W，波长 450~455 nm）下搅拌反 formed ex situ from dehydrogenative decarbonylation of hexane-1,6-
diol[J]. Organic & Biomolecular Chemistry, 2015, 13(3): 938-945.
应 20 h。制备了 11 个含不同取代基团的苯并咪唑
[17] MATTHEW K, NIELSEN B J, SHIELDS J, et al. Redox-neutral
[2,1-a]异喹啉-6(5H)-酮目标产物，产率为 48%~78%。 formylation of aryl chlorides through the photocatalytic generation of
该研究为合成苯并咪唑[2,1-a]异喹啉-6(5H)-酮类化 chlorine radicals[J]. Angewandte Chemie International Edition, 2017,
56(25): 7191-7194.
合物提供了一条绿色、简便的新方法。
[18] WU Y, GUO P, CHEN L, et al. Iron-catalyzed tandem oxidative
coupling and acetal hydrolysis reaction to prepare formylated
参考文献： benzothiazoles and isoquinolines[J]. Chemical Communications,
[1] LYGIN A V, MEIJERE A D. Isocyanides in the synthesis of nitrogen 2021, 57(26): 3271-3274.
heterocycles[J]. Angewandte Chemie International Edition, 2010, [19] ZHANG Y W (张益维), TANG J J (唐晶晶), WANG Y Q (王瑛琦),
49(18): 9094-9124. et al. Visible light promoting the synthesis of phosphinimides catalyzed
[2] PATIL N T, YAMAMOTO Y. Coinage metal-assisted synthesis of by TiO 2[J]. Fine Chemicals (精细化工), 2022, 39(1): 212-216.