Synthesis 2023; 55(17): 2639-2647
Reactions of Benzylboronate Nucleophiles
Timothy J. Barker∗
,
Andrew Bogatkevich
,
Dallas W. Crowder
,
Sophia G. Gierszal
,
Jacob C. Hayes
,
Michael R. Hollerbach
,
Richard W. Russell
Financial support is acknowledged from the National Center for Research Resources (5P20RR016461) and the National Institute of General Medical Sciences (8P20GM103499) from the NIH. Additional support was provided to M.R.H. by the Howard Hughes Medical Institute to the College of Charleston as part of their 2012 Undergraduate Science Education Competition and to S.G.G. from an Organic Syntheses PUI grant. The NMR spectrometer at the College of Charleston was supported by the National Science Foundation under Grant No. 1429308.
Abstract
This short review summarizes our laboratory’s development of benzylboronic esters as nucleophiles. Activation of the benzylboronic ester is achieved by irreversible coordination of an alkyllithium Lewis base to form a nucleophilic benzylboronate. This boronate was found to react with aldehydes, imines, ketones, and alkyl bromides. A copper catalyst was employed in reactions of the boronate with epoxides and aziridines.
1 Introduction
2 1,2-Additions
3 Additions to sp3 Electrophiles
4 Conclusion and Outlook
Key words
boron -
benzylation -
Lewis base -
copper -
boronate
Supporting Information
Supporting information for this article is available online at https://doi.org/10.1055/a-2072-2754.
Supporting Information
Publication History
Received: 09 March 2023
© 2023. Thieme. All rights reserved
Georg Thieme Verlag KG
References
1
Suzuki A.
Angew. Chem. Int. Ed. 2011; 50: 6722
2a
Partyka DV.
Chem. Rev. 2011; 111: 1529
2b
Qiao JX,
Lam PY. S.
Synthesis 2011; 829
2c
Wu X,
Anbarasan P,
Neumann H,
Beller M.
Angew. Chem. Int. Ed. 2010; 49: 9047
2d
Miyaura N.
Bull. Chem. Soc. Jpn. 2008; 81: 1535
2e
Xu L,
Zhang S,
Li P.
Chem. Soc. Rev. 2015; 44: 8848
2f
Molander GA,
Ellis N.
Acc. Chem. Res. 2007; 40: 275
2g
Li J,
Grillo AS,
Burke MD.
Acc. Chem. Res. 2015; 48: 2297
3a
Yang X,
Kalita SJ,
Maheshuni S,
Huang Y.-Y.
Coord. Chem. Rev. 2019; 392: 35
3b
Kalita SJ,
Cheng F,
Huang Y.-Y.
Adv. Synth. Catal. 2020; 362: 2778
3c
Friese FW,
Studer A.
Chem. Sci. 2019; 10: 8503
3d
Jana R,
Pathak TP,
Sigman MS.
Chem. Rev. 2011; 111: 1417
3e
Crudden CM,
Glasspoole BW,
Lata CJ.
Chem. Commun. 2009; 6704
3f
Doucet H.
Eur. J. Org. Chem. 2008; 2013
4a
Lachance H,
Hall DG.
Org. React. 2008; 73: 1
4b
Hall DG.
Synlett 2007; 1644
4c
Yus M,
Gonzalez-Gomez JC,
Foubelo F.
Chem. Rev. 2013; 113: 5595
4d
Diner C,
Szabo KJ.
J. Am. Chem. Soc. 2017; 139: 2
4e
Huo H.-X,
Duvall JR,
Huang M.-Y,
Hong R.
Org. Chem. Front. 2014; 1: 303
4f
Jonnalagadda SC,
Suman P,
Patel A,
Jampana G,
Colfer A.
Allylboration
. In
Boron Reagents in Synthesis
.
Coca A.
ACS Symposium Series 1236; American Chemical Society; Washington DC: 2016: 67
4g
Ramachandran PV,
Gagare PD,
Nicponski DR.
In
Comprehensive Organic Synthesis , 2nd ed., Vol. 2.
Knochel P,
Molander GA.
Elsevier; Amsterdam: 2014: 1
4h
Elford TG,
Hall DG.
In
Boronic Acids
.
Hall DG.
John Wiley & Sons; Hoboken: 2011: 393
5a
Sandford C,
Aggarwal VK.
Chem. Commun. 2017; 53: 5481
5b
Aiken SG,
Bateman JM,
Aggarwal VK.
In
Science of Synthesis: Advances in Organoboron Chemistry towards Organic Synthesis
.
Fernandez E.
Thieme; Stuttgart: 2020: 393
5c
Larouche-Gauthier R,
Elford TG,
Aggarwal VK.
J. Am. Chem. Soc. 2011; 133: 16794
6a
Leonori D,
Aggarwal VK.
Acc. Chem. Res. 2014; 47: 3174
6b
Tellis JC,
Kelly CB,
Primer DN,
Jouffroy M,
Patel NR,
Molander GA.
Acc. Chem. Res. 2016; 49: 1429
6c
Namirembe S,
Morken JP.
Chem. Soc. Rev. 2019; 48: 3464
6d
Reichle MA,
Breit B.
Angew. Chem. Int. Ed. 2012; 51: 5730
7
Pintaric C,
Olivero S,
Gimbert Y,
Chavant PY,
Dunach E.
J. Am. Chem. Soc. 2010; 132: 11825
8a
Atack TC,
Lecker RM,
Cook SP.
J. Am. Chem. Soc. 2014; 136: 9521
8b
Ito H,
Kubota K.
Org. Lett. 2012; 14: 890
8c
Yang C.-T,
Zhang Z.-Q,
Tajuddin H,
Wu C.-C,
Liang J,
Liu J.-H,
Fu Y,
Czyzewska M,
Steel PG,
Marder TB,
Liu L.
Angew. Chem. Int. Ed. 2012; 51: 528
8d
Murata M,
Oyama T,
Watanabe S,
Masuda Y.
Synth. Commun. 2002; 32: 2513
8e
Palmer WN,
Obligacion JV,
Pappas I,
Chirik PJ.
J. Am. Chem. Soc. 2016; 138: 766
9a
Stymiest JL,
Bagutski V,
French RM,
Aggarwal VK.
Nature 2008; 456: 778
9b
Mlynarski SN,
Karns AS,
Morken JP.
J. Am. Chem. Soc. 2012; 134: 16449
9c
Bagutski V,
Elford TG,
Aggarwal VK.
Angew. Chem. Int. Ed. 2011; 50: 1080
9d
Bonet A,
Odachowski M,
Leonori D,
Essafi S,
Aggarwal VK.
Nat. Chem. 2014; 6: 584
10a
Larsen MA,
Wilson CV,
Hartwig JF.
J. Am. Chem. Soc. 2015; 137: 8633
10b
Sueki S,
Kuninobu Y.
Org. Lett. 2013; 15: 1544
11
Feeney K,
Berionni G,
Mayr H,
Aggarwal VK.
Org. Lett. 2015; 17: 2614
12
Hollerbach MR,
Barker TJ.
Organometallics 2018; 37: 1425
13
Zou G,
Falck JR.
Tetrahedron Lett. 2001; 42: 5817
14
Sandford C,
Rasappan R,
Aggarwal VK.
J. Am. Chem. Soc. 2015; 137: 10100
15
Bose SK,
Brand S,
Omoregie HO,
Haehnel M,
Maier J,
Bringmann G,
Marder TB.
ACS Catal. 2016; 6: 8332
16 Barker, T. J.; Gierszal, S. G.; 2021 , unpublished results.
17
Hollerbach MR,
Hayes JC,
Barker TJ.
Eur. J. Org. Chem. 2019; 1646
18
Lee S,
Lee WM,
Yun J.
Adv. Synth. Catal. 2015; 357: 2219
19a
Li Y,
Zhou K,
Wen Z,
Cao S,
Shen X,
Lei M,
Gong L.
J. Am. Chem. Soc. 2018; 140: 15850
19b
Plasko DP,
Jordan CJ,
Ciesa BE,
Merrill MA,
Hanna JM. Jr.
Photochem. Photobiol. Sci. 2018; 17: 534
20
Buesking AW,
Baguley TD,
Ellman JA.
Org. Lett. 2011; 13: 964
21
Hayes JC,
Hollerbach MR,
Barker TJ.
Tetrahedron Lett. 2020; 61: 151505
22
Tatić T,
Hermann S,
Stalke D.
Organometallics 2012; 31: 5615
23
Dobson LS,
Pattison G.
Chem. Commun. 2016; 52: 11116
24
Russell RW,
Barker TJ.
Eur. J. Org. Chem. 2021; 2782
25a
Choi J,
Fu GC.
Science 2017; 356: eaaf7230
25b
Fu GC.
ACS Cent. Sci. 2017; 3: 692
25c
Wilsily A,
Tramutola F,
Owston NA,
Fu GC.
J. Am. Chem. Soc. 2012; 134: 5794
25d
Cherney AH,
Kadunce NT,
Reisman SE.
Chem. Rev. 2015; 115: 9587
26a
Murray B,
Zhao S,
Aramini JM,
Wang H,
Biscoe MR.
ACS Catal. 2021; 11: 2504
26b
Zhao S,
Gensch T,
Murray B,
Niemeyer ZL,
Sigman MS,
Biscoe MR.
Science 2018; 362: 670
26c
Li L,
Zhao S,
Joshi-Pangu A,
Diane M,
Biscoe MR.
J. Am. Chem. Soc. 2014; 136: 14027
26d
Lehmann JW,
Crouch IT,
Blair DJ,
Trobe M,
Wang P,
Li J,
Burke MD.
Nat. Commun. 2019; 10: 1263
27a
Grigg RD,
Rigoli JW,
Van Hoveln R,
Neale S,
Schomaker JM.
Chem. Eur. J. 2012; 18: 9391
27b
Takeda M,
Nagao K,
Ohmiya H.
Angew. Chem. Int. Ed. 2020; 59: 22460
28
Noh D,
Chea H,
Ju J,
Yun J.
Angew. Chem. Int. Ed. 2009; 48: 6062
29
Sorin G,
Martinez Mallorquin R,
Contie Y,
Baralle A,
Malacria M,
Goddard J.-P,
Fensterbank L.
Angew. Chem. Int. Ed. 2010; 49: 8721
30
Gierszal SG,
Barker TJ.
Tetrahedron Lett. 2021; 82: 153369
31a
Kjellgren J,
Aydin J,
Wallner OA,
Saltanova IV,
Szabó KJ.
Chem. Eur. J. 2005; 11: 5260
31b
Nielsen DK,
Doyle AG.
Angew. Chem. Int. Ed. 2011; 50: 6056
31c
Lu X.-Y,
Yan L.-Y,
Li J.-S,
Li J.-M,
Zhou H.-p,
Jiang R.-C,
Liu C.-C,
Lu R,
Hu R.
Chem. Commun. 2020; 56: 109
31d
Lu X.-Y,
Li J.-S,
Wang J.-Y,
Wang S.-Q,
Li Y.-M,
Zhu Y.-J,
Zhou R,
Ma W.-J.
RSC Adv. 2018; 8: 41561
31e
Lu X.-Y,
Yang C.-T,
Liu J.-H,
Zhang Z.-Q,
Lu X,
Lou X,
Xiao B,
Fu Y.
Chem. Commun. 2015; 51: 2388
32
Ebrahim-Alkhalil A,
Zhang Z.-Q,
Gong T.-J,
Su W,
Lu X.-Y,
Xiao B,
Fu Y.
Chem. Commun. 2016; 52: 4891
33
Alam M,
Wise C,
Baxter CA,
Cleator E,
Walkinshaw A.
Org. Process Res. Dev. 2012; 16: 435
34a
Dale JA,
Dull DL,
Mosher HS.
J. Org. Chem. 1969; 34: 2543
34b
Dale JA,
Mosher HS.
J. Am. Chem. Soc. 1973; 95: 512
35 Barker, T. J.; Crowder, D. W.; Gierszal, S. G. 2022 , unpublished results.
36
Jeong JU,
Tao B,
Sagasser I,
Henniges H,
Sharpless KB.
J. Am. Chem. Soc. 1998; 120: 6844
37
Bieber WL,
De Araújo CF. M.
Molecules 2002; 7: 902
38
Favero L,
Menichetti A,
Boldrini C,
Comparini LM,
Di Bussolo V,
Di Pietro S,
Pineschi M.
Molecules 2021; 26: 7399
39
Garcia-Ruiz C,
Chen JL. Y,
Sandford C,
Feeney K,
Lorenzo P,
Berionni G,
Mayr H,
Aggarwal VK.
J. Am. Chem. Soc. 2017; 139: 15324
40
Xu N,
Liang H,
Morken JP.
J. Am. Chem. Soc. 2022; 144: 11546
