Theoretical Study on Gold-catalyzed Cyclization of Alkynyl Benzodioxin to 8-Hydroxy-isocoumarin

doi:10.7503/cjcu20210157

Abstract

Abstract:

Density functional theory（DFT） calculations were carried out on the gold-catalyzed cyclization of alkynyl benzodioxin to 8-hydroxy-isocoumarin reaction to show the molecular mechanism of the reaction. The conclusions obtained from this work are different from those in the previous experimental study. The results show that water molecule acts as both the reactant and the proton shuttle， and promotes the reaction with gold complexes under mild conditions. The nucleophilic addition site of water on the substrate is the C（sp³） atom on the side of the substrate far away from the oxabenzene ring， resulting in C（sp³）—O bond breaking in the substrate. The formation of new C—O bond and the cleavage of C—O bond in the substrate follow a step-by-step mechanism. The oxygen in the side-product acetone comes from the contribution of water in the reaction system. The regioselectivity of the reaction originates from the polarization of alkynyl π-electrons induced by substituents.

Key words: Gold catalysis, Density functional theory, Alkynyl benzodioxin, Cycloisomerization, Reaction mechanism

CLC Number:

O641

TrendMD:

YANG Yiying, ZHU Rongxiu, ZHANG Dongju, LIU Chengbu. Theoretical Study on Gold-catalyzed Cyclization of Alkynyl Benzodioxin to 8-Hydroxy-isocoumarin[J]. Chem. J. Chinese Universities, 2021, 42(7): 2299.

Figures/Tables 8

References 32

1	Pal S.， Chatare V.， Pal M.， Curr. Org. Chem.， 2011， 15， 782—800
2	Nakhi A.， Adepu R.， Rambabu D.， Kishore R.， Vanaja G. R.， Kalle A. M.， Pal M.， Bioorg. Med. Chem. Lett.， 2012， 22， 4418— 4427
3	Devienne K. F.， Calgaro⁃Helena A. F.， Dorta D. J.， Prado I. M. R.， Raddi M. S. G.， Vilegas W.， Uyemura S. A.， Santos A. C.， Curti C.， Phytochemistry， 2007， 68， 1075—1080
4	Widelski J.， Graikou M. K.， Glowniak K.， Chinou I.， Molecules， 2009， 14， 2729—2734
5	Brasholz M.， Sorgel S.， Azap C.， Reibig H. U.， Eur. J. Org. Chem.， 2007， 3801—3814
6	Ola A. R. B.， Thomy D.， Lai D.， Brötz⁃Oesterhelt H.， Proksch P.， J. Nat. Prod.， 2013， 76， 2094—2099
7	Kurume A.， Kamata Y.， Yamashita M.， Wang Q.， Matsuda H.， Yoshikawa M.， Kawasaki I.， Ohta S.， Chem. Pharm. Bull.， 2008， 56， 1264—1269
8	Mali R. S.， Babu K. N.， Jagtap P. G.， J. Chem. Soc.， Perkin Trans. 1.， 2001， 3017—3019
9	Son J. Y.， Maeng C.， Lee P. H.， Bull. Korean Chem. Soc.， 2020， 41， 388—399
10	Sudarshan K.， Manna M. K.， Aidhen I. S.，Eur. J. Org. Chem.， 2015， 1797—1803
11	Cai S.， Wang F.， Xi C.， J. Org. Chem.， 2012， 77， 2331—2336
12	Speranca A.， Godoi B.， Pinton S.， Back D. F.， Menezes P. H.， Zeni G.， J. Org. Chem.， 2011， 76， 6789—6797
13	Mallampudi N. A.， Reddy G. S.， Maity S.， Mohapatra D. K.， Org. Lett.， 2017， 19， 2074—2077
14	Frisch M. J.， Trucks G. W.， Schlegel H. B.， Scuseria G. E.， Robb M. A.， Cheeseman J. R.， Scalmani G.， Barone V.， Mennucci B.， Petersson G. A.， Nakatsuji H.， Caricato M.， Li X.， Hratchian H. P.， Izmaylov A. F.， Bloino J.， Zheng G.， Sonnenberg J. L.， Hada M.， Ehara M.， Toyota K.， Fukuda R.， Hasegawa J.， Ishida M.， Nakajima T.， Honda Y.， Kitao O.， Nakai H.， Vreven T.， Montgomery J. A. Jr.， Peralta J. E.， Ogliaro F.， Bearpark M.， Heyd J. J.， Brothers E.， Kudin K. N.， Staroverov V. N.， Kobayashi R.， Normand J.， Raghavachari K.， Rendell A.， Burant J. C.， Iyengar S. S.， Tomasi J.， Cossi M.， Rega N.， Millam N. J.， Klene M.， Knox J. E.， Cross J. B.， Bakken V.， Adamo C.， Jaramillo J.， Gomperts R.， Stratmann R. E.， Yazyev O.， Austin A. J.， Cammi R.， Pomelli C.， Ochterski J. W.， Martin R. L.， Morokuma K.， Zakrzewski V. G.， Voth G. A.， Salvador P.， Dannenberg J. J.， Dapprich S.， Daniels A. D.， Farkas O.， Foresman J. B.， Ortiz J. V.， Cioslowski J.， Fox D. J.， Gaussian 09， Revision B.01， Gaussian Inc.， Wallingford CT， 2010
15	Tapia O. J.， Math. Chem.， 1992， 10， 139—181
16	Tomasi J.， Persico M.， Chem. Rev.， 1994， 94， 2027—2094
17	Zhao Y.， Truhlar D. G.， Acc. Chem. Res.， 2008， 41， 157—167
18	Zhao Y.， Truhlar D. G.， Theor. Chem. Acc.， 2008， 120， 215—241
19	Hay P. J.， Wadt W. R.， J. Chem. Phys.， 1985， 82， 299—310
20	Ehlers A. W.， Böhme M.， Dapprich S.， Gobbi A.， Höllwarth A.， Jonas V.， Köhler K. F.， Stegmann R.， Veldkamp A.， Frenking G.， Chem. Phys. Lett.， 1993， 208， 111—114
21	Huzinaga S.， Comput. Phys. Rep.， 1985， 2， 281—339
22	Bhattacharjee R.， Nijamudheen A.， Datta A.， Org. Biomol. Chem.， 2015， 13， 7412—7420
23	Fukui K.， Acc. Chem. Res.， 1981， 14， 363—368
24	Reed A. E.， Weinstock R. B.， Weinhold F.， J. Chem. Phys.， 1985， 83， 735—746
25	Glendening E. D.， Reed A. E.， Carpenter J. E.， Weinhold F.， NBO， Version 3.1， Gaussian Inc.， Wallingford CT， 2010
26	Legault C. Y.， CYLview， 1.0b， Université de Sherbrooke， Sherbrooke， 2009（www.cylview.org）
27	Ess D. H.， Houk K. N.， J. Am. Chem. Soc.，2007， 129， 10646—10647
28	Ess D. H.， Houk K. N.， J. Am. Chem. Soc.， 2008， 130， 10187—10198
29	Pedley J. B.， Naylor R. D.， Kirby S. P.， Thermochemical Data of Organic Compounds， 2nd Ed.， Chapman and Hall， New York， 1986
30	Mulder P.， Mozenson O.， Lin S.， Bernardes C. E. S.， Minas da Piedade M. E.， Santos A. F. L. O.， Ribeiro da Silva M. A. V.， Dilabio G. A.， Korth H. G.， Ingold K. U.， J. Phys. Chem. A， 2006， 110， 9949—9958
31	Kozuch S.， Shaik S.， Acc. Chem. Res.， 2011， 44， 101—110
32	Kozuch S.， Shaik S.， J. Am. Chem. Soc.， 2006， 128， 3355—3365

Transition state	?E^≠^a/（kJ·mol^-1）	?E^b_dist?cat/（kJ·mol^-1）	?E^c_dist?sub/（kJ·mol^-1）	?E^d_dist/（kJ·mol^-1）	?E^e_int/（kJ·mol^-1）
TS1	63.5	12.9	151.6	164.6	-101.1
TS2	23.6	1.5	105.8	107.3	-83.7

Transition state	?E^≠^a/（kJ·mol^-1）	?E^b_dist?cat/（kJ·mol^-1）	?E^c_dist?sub/（kJ·mol^-1）	?E^d_dist/（kJ·mol^-1）	?E^e_int/（kJ·mol^-1）
TS1	63.5	12.9	151.6	164.6	-101.1
TS2	23.6	1.5	105.8	107.3	-83.7

[1]	HE Hongrui, XIA Wensheng, ZHANG Qinghong, WAN Huilin. Density-functional Theoretical Study on the Interaction of Indium Oxyhydroxide Clusters with Carbon Dioxide and Methane [J]. Chem. J. Chinese Universities, 2022, 43(8): 20220196.
[2]	ZHOU Zixuan, YANG Haiyan, SUN Yuhan, GAO Peng. Recent Progress in Heterogeneous Catalysts for the Hydrogenation of Carbon Dioxide to Methanol [J]. Chem. J. Chinese Universities, 2022, 43(7): 20220235.
[3]	YANG Dan, LIU Xu, DAI Yihu, ZHU Yan, YANG Yanhui. Research Progress in Electrocatalytic CO₂ Reduction Reaction over Gold Clusters [J]. Chem. J. Chinese Universities, 2022, 43(7): 20220198.
[4]	WONG Honho, LU Qiuyang, SUN Mingzi, HUANG Bolong. Rational Design of Graphdiyne-based Atomic Electrocatalysts： DFT and Self-validated Machine Learning [J]. Chem. J. Chinese Universities, 2022, 43(5): 20220042.
[5]	SUN Cuihong, LYU Liqiang, LIU Ying, WANG Yan, YANG Jing, ZHANG Shaowen. Mechanism and Kinetics on the Reaction of Isopropyl Nitrate with Cl， OH and NO₃ Radicals [J]. Chem. J. Chinese Universities, 2022, 43(2): 20210591.
[6]	LIU Yang, LI Wangchang, ZHANG Zhuxia, WANG Fang, YANG Wenjing, GUO Zhen, CUI Peng. Theoretical Exploration of Noncovalent Interactions Between Sc₃C₂@C₈₀ and ［12］Cycloparaphenylene Nanoring [J]. Chem. J. Chinese Universities, 2022, 43(11): 20220457.
[7]	CHENG Yuanyuan, XI Biying. Theoretical Study on the Fragmentation Mechanism of CH₃SSCH₃ Radical Cation Initiated by OH Radical [J]. Chem. J. Chinese Universities, 2022, 43(10): 20220271.
[8]	ZHOU Chengsi, ZHAO Yuanjin, HAN Meichen, YANG Xia, LIU Chenguang, HE Aihua. Regulation of Silanes as External Electron Donors on Propylene/butene Sequential Polymerization [J]. Chem. J. Chinese Universities, 2022, 43(10): 20220290.
[9]	WANG Yuanyue, AN Suosuo, ZHENG Xuming, ZHAO Yanying. Spectroscopic and Theoretical Studies on 5-Mercapto-1，3，4-thiadiazole-2-thione Microsolvation Clusters [J]. Chem. J. Chinese Universities, 2022, 43(10): 20220354.
[10]	ZHONG Shengguang, XIA Wensheng, ZHANG Qinghong, WAN Huilin. Theoretical Study on Direct Conversion of CH₄ and CO₂ into Acetic Acid over MCu₂O_x（M = Cu²⁺， Ce⁴⁺， Zr⁴⁺） Clusters [J]. Chem. J. Chinese Universities, 2021, 42(9): 2878.
[11]	MA Lijuan, GAO Shengqi, RONG Yifei, JIA Jianfeng, WU Haishun. Theoretical Investigation of Hydrogen Storage Properties of Sc， Ti， V-decorated and B/N-doped Monovacancy Graphene [J]. Chem. J. Chinese Universities, 2021, 42(9): 2842.
[12]	MENG Fanwei, GAO Qi, YE Qing, LI Chenxi. Potassium Poisoning Mechanism of Cu-SAPO-18 Catalyst for Selective Catalytic Reduction of NO_x by Ammonia [J]. Chem. J. Chinese Universities, 2021, 42(9): 2832.
[13]	HUANG Luoyi, WENG Yueyue, HUANG Xuhui, WANG Chaojie. Theoretical Study on the Structures and Properties of Flavonoids in Plantain [J]. Chem. J. Chinese Universities, 2021, 42(9): 2752.
[14]	ZHAO Ke, HONG Zhi, ZHANG Liming. Applications of Bifunctional Biaryl-2-ylphosphine Ligands in Asymmetric Gold Catalysis [J]. Chem. J. Chinese Universities, 2021, 42(8): 2324.
[15]	ZHENG Ruoxin, ZHANG Igor Ying, XU Xin. Development and Benchmark of Lower Scaling Doubly Hybrid Density Functional XYG3 [J]. Chem. J. Chinese Universities, 2021, 42(7): 2210.