钯催化2-溴-1,3,5-三甲基苯和异丙基硼酸Suzuki-Miyaura偶联反应中配体对产物选择性调控的理论研究
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摘要
采用密度泛函理论(DFT)计算,我们研究了钯催化2-溴-1,3,5-三甲基苯和异丙基硼酸发生Suzuki-Miyaura偶联反应的机理,并考察了催化剂中的膦配体对产物选择性的影响.计算结果表明,反应机理主要包含3个步骤,涉及氧化加成、转金属化和还原消除.与没有碱基和水参与的反应相比,转金属化步骤在K_3PO_4和水的辅助下更容易发生.根据Shaik等提出的能量跨度模型, 5c是反应的决速中间体,还原消除步骤中生成产物的过渡态是反应的决速过渡态,并决定了反应产物的选择性.此偶联反应能够生成3种产物,理论计算表明, product-1是主要产物,product-2和product-3是次要产物,这与实验的数据是一致的.进一步计算表明,采用大配体钯催化剂可以抑制异构化和还原副反应,有利于生成期待的产物product-1.
Pd-catalyzed Suzuki-Miyaura cross-coupling reaction mechanism between sterically hindered 2-bromo-1,3,5-trimethylbenzene and isopropylboronic acid has been investigated by the density functional theory(DFT)calculations. The computations demonstrated that the mechanism is composed of three steps, oxidative addition,transmetalation, and reductive elimination. Comparing the base-and water-free process, the transmetalation step withthe assistance of K_3PO_4 and water is significantly more facile. According to the energetic span model, 5c is TOFdetermining intermediate, and the transition states in reductive elimination are TOF determining transition states.Reductive elimination step determines the product selectivity. The cross-coupling reaction can generate three differentproducts, and the calculations revealed that product-1 is the major product, product-2 and product-3 are the minorproducts, which are consistent with experimental data. Further calculations elucidated that the bulky ligand may inhibit isomerization and reduction side reactions and facilitate the generation of product-1.
Pd-catalyzed Suzuki-Miyaura cross-coupling reaction mechanism between sterically hindered 2-bromo-1,3,5-trimethylbenzene and isopropylboronic acid has been investigated by the density functional theory(DFT)calculations. The computations demonstrated that the mechanism is composed of three steps, oxidative addition,transmetalation, and reductive elimination. Comparing the base-and water-free process, the transmetalation step withthe assistance of K_3PO_4 and water is significantly more facile. According to the energetic span model, 5c is TOFdetermining intermediate, and the transition states in reductive elimination are TOF determining transition states.Reductive elimination step determines the product selectivity. The cross-coupling reaction can generate three differentproducts, and the calculations revealed that product-1 is the major product, product-2 and product-3 are the minorproducts, which are consistent with experimental data. Further calculations elucidated that the bulky ligand may inhibit isomerization and reduction side reactions and facilitate the generation of product-1.
引文
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72 Hong X,Wang J,Yang YF,He L,Ho CY,Houk KN.ACS Catal,2015,5:5545-5555
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2 Xu G,Zhao Q,Tang W.Chin J Org Chem,2014,34:1919-1940
3 Li C,Xiao G,Zhao Q,Liu H,Wang T,Tang W.Org Chem Front,2014,1:225-229
4 Miyaura N,Suzuki A.Chem Rev,1995,95:2457-2483
5 Miyaura N.Top Curr Chem,2002,219:11-59
6 Johansson Seechurn CCC,Kitching MO,Colacot TJ,Snieckus V.Angew Chem Int Ed,2012,51:5062-5085
7 Barder TE,Walker SD,Martinelli JR,Buchwald SL.J Am Chem Soc,2005,127:4685-4696
8 Littke AF,Fu GC.Angew Chem Int Ed,2002,41:4176-4211
9 Han FS.Chem Soc Rev,2013,42:5270-5298
10 Tasker SZ,Standley EA,Jamison TF.Nature,2014,509:299-309
11 Li Z,Liu L.Chin J Catal,2015,36:3-14
12 Wang XX,Luo MJ,Lu JM.Org Biomol Chem,2015,13:11438-11444
13 Xiong Y,Huang T,Ji X,Wu J,Cao S.Org Biomol Chem,2015,13:7389-7392
14 Weires NA,Baker EL,Garg NK.Nat Chem,2015,8:75-79
15 Xu ZY,Yu HZ,Fu Y.Chem Asian J,2017,12:1765-1772
16 Harris MR,Hanna LE,Greene MA,Moore CE,Jarvo ER.J Am Chem Soc,2013,135:3303-3306
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18 Xie H,Li Y,Wang L,Kuang J,Lei Q,Fang W.Dalton Trans,2017,46:13010-13019
19 Dreher SD,Dormer PG,Sandrock DL,Molander GA.J Am Chem Soc,2008,130:9257-9259
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24 Vila C,Giannerini M,Hornillos V,Fa?anás-Mastral M,Feringa BL.Chem Sci,2014,5:1361-1367
25 Li C,Chen T,Li B,Xiao G,Tang W.Angew Chem Int Ed,2015,54:3792-3796
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27 Zhao Y,Truhlar DG.J Phys Chem A,2006,110:5121-5129
28 Zhao Y,Truhlar DG.J Phys Chem A,2006,110:13126-13130
29 Melvin PR,Nova A,Balcells D,Hazari N,Tilset M.Organometallics,2017,36:3664-3675
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31 Han L,Liu T.Org Biomol Chem,2017,15:5055-5061
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33 Ren Y,Yan C,Jia J,Wu HS.J Organomet Chem,2016,824:88-98
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43 Sharma AK,Joshi H,Bhaskar R,Kumar S,Singh AK.Dalton Trans,2017,46:2485-2496
44 Begum T,Mondal M,Borpuzari MP,Kar R,Kalita G,Gogoi PK,Bora U.Dalton Trans,2017,46:539-546
45 Gu S,Du J,Huang J,Guo Y,Yang L,Xu W,Chen W.Dalton Trans,2017,46:586-594
46 Lennox AJJ,Lloyd-Jones GC.Chem Soc Rev,2014,43:412-443
47 Duong HA,Wu W,Teo YY.Organometallics,2017,36:4363-4366
48 Lei P,Meng G,Ling Y,An J,Szostak M.J Org Chem,2017,82:6638-6646
49 Ji CL,Hong X.J Am Chem Soc,2017,139:15522-15529
50 Li Z,Zhang SL,Fu Y,Guo QX,Liu L.J Am Chem Soc,2009,131:8815-8823
51 Xu L,Chung LW,Wu YD.ACS Catal,2016,6:483-493
52 Yu DG,Shi ZJ.Angew Chem Int Ed,2011,50:7097-7100
53 Liu L,Zhang S,Chen H,Lv Y,Zhu J,Zhao Y.Chem Asian J,2013,8:2592-2595
54 Hong X,Liang Y,Houk KN.J Am Chem Soc,2014,136:2017-2025
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56 Xue L,Lin Z.Chem Soc Rev,2010,39:1692-1705
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58 Carrow BP,Hartwig JF.J Am Chem Soc,2011,133:2116-2119
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60 Antoft-Finch A,Blackburn T,Snieckus V.J Am Chem Soc,2009,131:17750-17752
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62 Jezorek RL,Zhang N,Leowanawat P,Bunner MH,Gutsche N,Pesti AKR,Olsen JT,Percec V.Org Lett,2014,16:6326-6329
63 Lou S,Fu GC.Adv Synth Catal,2010,352:2081-2084
64 Dallas AS,Gothelf KV.J Org Chem,2005,70:3321-3323
65 Liang Y,Zhou H,Yu ZX.J Am Chem Soc,2009,131:17783-17785
66 Shi FQ,Li X,Xia Y,Zhang L,Yu ZX.J Am Chem Soc,2007,129:15503-15512
67 Guan BT,Wang Y,Li BJ,Yu DG,Shi ZJ.J Am Chem Soc,2008,130:14468-14470
68 Quasdorf KW,Antoft-Finch A,Liu P,Silberstein AL,Komaromi A,Blackburn T,Ramgren SD,Houk KN,Snieckus V,Garg NK.J Am Chem Soc,2011,133:6352-6363
69 Tang S,Eisenstein O,Nakao Y,Sakaki S.Organometallics,2017,36:2761-2771
70 Singh V,Nakao Y,Sakaki S,Deshmukh MM.J Org Chem,2017,82:289-301
71 Gao Y,Houk KN,Ho CY,Hong X.Org Biomol Chem,2017,15:7131-7139
72 Hong X,Wang J,Yang YF,He L,Ho CY,Houk KN.ACS Catal,2015,5:5545-5555
73 Jiang YY,Li Z,Shi J.Organometallics,2012,31:4356-4366
74 Zell D,Bursch M,Müller V,Grimme S,Ackermann L.Angew Chem Int Ed,2017,56:10378-10382
75 Kozuch S,Shaik S.Acc Chem Res,2011,44:101-110
76 Kozuch S,Martin JML.Chem Commun,2011,47:4935-4937
77 Liu G,Xu G,Luo R,Tang W.Synlett,2013,19:2465-2471
78 Martin R,Buchwald SL.Acc Chem Res,2008,41:1461-1473
79 Clavier H,Nolan SP.Chem Commun,2010,46:841-861
80 Bruckmann J,Krüger C.Acta Crystlogr C Cryst Struct Commun,1995,51:1155-1158
81 Luo X,Li Y,Qi X,Zhu L,Chen C,Lan Y.Sci Sin Chim,2017,47:341-349