Iron-Catalysed C(sp2)-H Borylation Enabled by Carboxylate Activation

被引：29

作者：

Britton, Luke ^{[1
]}

Docherty, Jamie H. ^{[1
]}

Dominey, Andrew P. ^{[2
]}

Thomas, Stephen P. ^{[1
]}

机构：

[1] Univ Edinburgh, EaStCHEM Sch Chem, Joseph Black Bldg,David Brewster Rd, Edinburgh EH9 3FJ, Midlothian, Scotland

[2] GSK Med Res Ctr, Gunnels Wood Rd, Stevenage SG1 2NY, Herts, England

来源：

MOLECULES | 2020年 / 25卷 / 04期

基金：

英国工程与自然科学研究理事会;

关键词：

catalysis; borylation; Iron; C-H functionalisation; pinacolborane; photochemistry; C-H BORYLATION; BOND FUNCTIONALIZATION; METAL-CATALYSTS; ARENES; THIOPHENES; REDUCTION; VERSATILE;

D O I：

10.3390/molecules25040905

中图分类号：

Q5 [生物化学]; Q7 [分子生物学];

学科分类号：

071010 ; 081704 ;

摘要：

Arene C(sp(2))-H bond borylation reactions provide rapid and efficient routes to synthetically versatile boronic esters. While iridium catalysts are well established for this reaction, the discovery and development of methods using Earth-abundant alternatives is limited to just a few examples. Applying an in situ catalyst activation method using air-stable and easily handed reagents, the iron-catalysed C(sp(2))-H borylation reactions of furans and thiophenes under blue light irradiation have been developed. Key reaction intermediates have been prepared and characterised, and suggest two mechanistic pathways are in action involving both C-H metallation and the formation of an iron boryl species.

引用

页数：11

共 49 条

[1] Regiodivergent hydrosilylation, hydrogenation, [2π+2π]-cycloaddition and C-H borylation using counterion activated earth-abundant metal catalysis [J].

Agahi, Riaz ;

Challinor, Amy J. ;

Dunne, Joanne ;

Docherty, Jamie H. ;

Carter, Neil B. ;

Thomas, Stephen P. .

CHEMICAL SCIENCE, 2019, 10 (19) :5079-5084

[2] Addition of CO2 to alkyl iron complexes, Fe(PP)2Me2 [J].

Allen, Olivia R. ;

Dalgarno, Scott J. ;

Field, Leslie D. ;

Jensen, Paul ;

Tumbull, Anthony J. ;

Willis, Anthony C. .

ORGANOMETALLICS, 2008, 27 (09) :2092-2098

[3] PHOTOCHEMICAL-REACTIONS OF [CIS-FE(H)(2)(ME(2)PCH(2)CH2(P)ME(2))(2)] WITH THIOPHENES - INSERTION INTO C-H AND C-S BONDS [J].

BUYS, IE ;

FIELD, LD ;

HAMBLEY, TW ;

MCQUEEN, AED .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1994, (05) :557-558

[4] Iron-Catalyzed C-H Functionalization Processes [J].

Cera, Gianpiero ;

Ackermann, Lutz .

TOPICS IN CURRENT CHEMISTRY, 2016, 374 (05)

[5] Iridium-catalyzed borylation of thiophenes: versatile, synthetic elaboration founded on selective C-H functionalization [J].

Chotana, Ghayoor A. ;

Kallepalli, Venkata A. ;

Maleczka, Robert E., Jr. ;

Smith, Milton R., III .

TETRAHEDRON, 2008, 64 (26) :6103-6114

[6] Recent Advances in C-H Functionalization [J].

Davies, Huw M. L. ;

Morton, Daniel .

JOURNAL OF ORGANIC CHEMISTRY, 2016, 81 (02) :343-350

[7]

Docherty JH, 2017, NAT CHEM, V9, P595, DOI [10.1038/NCHEM.2697, 10.1038/nchem.2697]

[8] Iron-Catalyzed C-H Borylation of Arenes [J].

Dombray, Thomas ;

Werncke, C. Gunnar ;

Jiang, Shi ;

Grellier, Mary ;

Vendier, Laure ;

Bontemps, Sebastien ;

Sortais, Jean-Baptiste ;

Sabo-Etienne, Sylviane ;

Darcel, Christophe .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2015, 137 (12) :4062-4065

[9] Evaluation of Organic Hydride Donors as Reagents for the Reduction of Carbon Dioxide and Metal-Bound Formates [J].

Elton, Timothy E. ;

Ball, Graham E. ;

Bhadbhade, Mohan ;

Field, Leslie D. ;

Colbran, Stephen B. .

ORGANOMETALLICS, 2018, 37 (21) :3972-3982

[10] Nickel-catalyzed borylation of arenes and indoles via C-H bond cleavage [J].

Furukawa, Takayuki ;

Tobisu, Mamoru ;

Chatani, Naoto .

CHEMICAL COMMUNICATIONS, 2015, 51 (30) :6508-6511

← 1 2 3 4 5 →