Recent Progress in Transition-Metal-Catalyzed Asymmetric C—H Borylation

doi:10.6023/cjoc202308001

Abstract

Transition-metal-catalyzed asymmetric C—H borylation is one of the most powerful strategies for the construction of chiral organoborate compounds, which has attracted extensive attention in the fields of synthetic chemistry, medicinal chemistry and materials science due to its atom- and step-economy. The design and synthesis of novel chiral ligands are essential for the success of asymmetric C—H borylation. Based on the design and development of chiral ligands, the recent progress of transition-metal-catalyzed asymmetric C(sp²)—H and C(sp³)—H borylation reactions is summarized.

Key words: asymmetric C—H borylation, chiral ligand, transition metal complex

Cite this article

Wenfang Wang. Recent Progress in Transition-Metal-Catalyzed Asymmetric C—H Borylation[J]. Chinese Journal of Organic Chemistry, 2023, 43(9): 3146-3166.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 32

Scheme 1. Asymmetric C(sp2)—H borylation and C(sp3)—H borylation

Scheme 2. A general catalytic cycle for the borylation of aryl C(sp2)—H catalyzed by an iridium catalyst

Scheme 3. Silyl-directed iridium-catalyzed enantioselective borylation of aryl C—H bonds

Scheme 4. Enantioselective borylation of aryl C—H bonds catalyzed by iridium/Py-DHIQ system

Scheme 5. Enantioselective borylation of aryl C—H bonds catalyzed by achiral bidentate N,B ligand/iridium system and novel chiral bidentate N,B ligand skeleton

Scheme 6. Chiral N,B-bidentate ligand enabled iridium-cata- lyzed asymmetric C(sp2)—H borylation

Scheme 7. Representative substrate scope of enantioselective C(sp2)—H borylation of prochiral diarylmethylamines

Entry	R¹, R², R³	Conv./%	ee(6')/%	ee(5')/%	s^a
1	CF₃, CF₃, H	30	94	41	68
2	CF₃, CF₃, 3-Me	30	90	40	25
3	OMe, OMe, H	33	85	42	19
4	OMe, CF₃, 3-Cl	50	88	88	45
5	CF₃, CF₃, 4-Cl	54	72	62	9

Table 1. Representative substrate scope of kinetic resolution of C(sp2)—H borylation of racemic diarylmethylamines

Scheme 8. Representative substrate scope of enantioselective C(sp2)—H borylation of prochiral diarylphosphinates

Scheme 9. Representative substrate scope of enantioselective C(sp2)—H borylation catalyzed by iridium/L6 system

Entry	B₂pin₂/equiv.	10a∶I∶II∶III^a	Yield^a/%	ee^b/%
1	1.00	87.6∶0.0∶9.9∶2.5	91 (83)^c	92
2	0.50	98.8∶0.0∶1.2∶0.0	65	87
3	0.75	96.2∶0.0∶3.1∶0.7	88	88
4	1.30	57.7∶0.0∶38.8∶3.5	53 (52)^c	96

Table 2. Effect of B2pin2 dosage on enantioselective C(sp2)—H borylation of benzhydryl ethers

Scheme 10. Representative substrate scope of iridium/L7 system catalyzed enantioselective C(sp2)—H borylation

Scheme 11. Anionic ligands, chiral cation, ion-paired complexes and enantioselective remote C(sp2)—H borylation

Scheme 12. Representative substrate scope of enantioselective C(sp2)—H borylation of benzhydrylamides and diaryl phosphinamides

Figure 1. Chiral pyridine-type ligands CP1 and CP5 and chiral pyridine-derived bidentate N,B-ligands skeleton

Scheme 13. Representative substrate scope of triarylmethanes

Scheme 14. Representative substrate scope of ferrocene

Scheme 15. Pd(II)-catalyzed enantioselective borylation of methylene C(sp3)—H in cyclic substrates

Scheme 16. Iridium-catalyzed enantioselective C(sp3)—H borylation of cyclobutanes

Scheme 17. Iridium-catalyzed enantioselective C(sp3)—H borylation of cyclopropanecarboxamides

Scheme 18. Synthesis of Levomilnacipran through C—B bond conversion

Scheme 19. [Ir(OMe)(cod)]2/L13 system catalyzed enantioselective C(sp3)—H borylation of aminocyclopropanes

Scheme 20. [Ir(cod)Cl]2/L14 system catalyzed enantioselective C(sp3)—H borylation of aminocyclopropanes

Scheme 21. [Ir(cod)Cl]2/L14 system catalyzed enantioselective C(sp3)—H borylation of cyclopropanol derivatives

Scheme 22. Ir—O bridging catalytic hypothesis

Scheme 23. Iridium-catalyzed enantioselective C(sp3)—H borylation of ether cyclopropane

Scheme 24. Iridium-catalyzed enantioselective C(sp3)—H borylation of THIQ

Scheme 25. Iridium-catalyzed enantioselective C(sp3)—H borylation of azacycles

Scheme 26. Iridium-catalyzed enantioselective C(sp3)—H borylation of pyrazoles

Scheme 27. Iridium-catalyzed enantioselective C(sp3)—H borylation of acyclic amides

Scheme 28. Cobalt-catalyzed asymmetric remote C(sp3)—H borylation of internal alkenes via alkene isomerization

Scheme 29. Cobalt-catalyzed asymmetric remote C(sp3)—H borylation of alkyl halides

References 47

[1]	(a) Sun H.-Y.; Hall D. G. In Synthesis and Application of Organoboron Compounds, Eds.: Fernandez, E.; Whiting, A., Springer International, Cham, 2015, p. 221.
	(b) Leonori D.; Aggarwal V. K. In Synthesis and Application of Organoboron Compounds, Eds.: Fernandez, E.; Whiting, A., Springer International, Cham, 2015, p. 271.
	(c) Jakle F. In Synthesis and Application of Organoboron Compounds, Eds.: Fernandez, E.; Whiting, A., Springer International, Cham, 2015, p. 297.
	(d) Wang M.; Shi Z. Chem. Rev. 2020, 120, 7348. doi: 10.1021/acs.chemrev.9b00384
	(e) Hall D. G. Boronic Acids: Preparation and Applications in Organic Synthesis Medicine and Materials, Ed.: Hall, D. G., Wiley-VCH, Weinheim, 2011. p. 28.
	(f) Cui P.-F.; Gao Y.; Guo S.-T.; Jin G.-X. Chin. J. Chem. 2021, 39, 281. doi: 10.1002/cjoc.v39.2
	(g) Wang Q.-T.; Meng W.; Feng X.-Q.; Du H.-F. Chin. J. Chem. 2021, 39, 918. doi: 10.1002/cjoc.v39.4
[2]	Xie T.; Chen L.-L.; Shen Z.-L; Xu S.-M. Angew. Chem., Int. Ed. 2023, 62, e202300199.
[3]	Su B.; Zhou T.-G.; Xu P.-L.; Shi Z.-J.; Hartwig J. F. Angew. Chem., Int. Ed. 2017, 56, 7205.
[4]	Shi Y.-J.; Gao Q.; Xu S.-M. J. Am. Chem. Soc. 2019, 141, 10599. doi: 10.1021/jacs.9b04549
[5]	Dick L. R.; Fleming P. E. Drug Discovery Today 2010, 15, 243. doi: 10.1016/j.drudis.2010.01.008
[6]	Adams J.; Kauffman M. Cancer Invest. 2004, 22, 304. doi: 10.1081/CNV-120030218
[7]	Gentile M.; Offidani M.; Vigna E.; Corvatta L.; Recchia A. G.; Morabito L.; Morabito F.; Gentili S. Expert Opin. Invest. Drugs 2015, 24, 1287. doi: 10.1517/13543784.2015.1065250
[8]	Gallerani E.; Zucchetti M.; Brunelli D.; Marangon E.; Noberasco C.; Hess D.; Delmonte A.; Martinelli G.; Bohm S.; Driessen C.; De Braud F.; Marsoni S.; Cereda R.; Sala F.; D'Incalci M.; Sessa C. Eur. J. Cancer 2013, 49, 290. doi: 10.1016/j.ejca.2012.09.009 pmid: 23058787
[9]	Roemmele R. C.; Christie M. A. Org. Process Res. Dev. 2013, 17, 422. doi: 10.1021/op400010u
[10]	(a) Jin S.; Zhu C.; Li M.; Wang B. Bioorg. Med. Chem. Lett. 2009, 19, 1596. doi: 10.1016/j.bmcl.2009.02.011
	(b) Jin S.; Zhu C.; Cheng Y.; Li M.; Wang B. Bioorg. Med. Chem. 2010, 18, 1449. doi: 10.1016/j.bmc.2010.01.017
[11]	Andres P.; Ballano G.; Calaza M. I.; Cativiela C. Chem. Soc. Rev. 2016, 45, 2291. doi: 10.1039/C5CS00886G
[12]	(a) Brown H. C.; Cole T. E. Organometallics 1983, 2, 1316. doi: 10.1021/om50004a009 pmid: 17849483
	(b) Burgess K.; Van der Donk W. A.; Westcott S. A.; Marder T. B.; Baker R. T.; Calabrese J. C. J. Am. Chem. Soc. 1992, 114, 9350. doi: 10.1021/ja00050a015 pmid: 17849483
	(c) Crudden C. M.; Edwards D. Eur. J. Org. Chem. 2003, 2003, 4695. doi: 10.1002/ejoc.v2003:24 pmid: 17849483
	(d) Burgess K.; Ohlmeyer M. J. Chem. Rev. 1991, 91, 1179. doi: 10.1021/cr00006a003 pmid: 17849483
	(e) Matteson D. S.; Sadhu K. M.; Lienhard G. E. J. Am. Chem. Soc. 1981, 103, 5241. doi: 10.1021/ja00407a051 pmid: 17849483
	(f) Matteson D. S. Chem. Rev. 1989, 89, 1535. doi: 10.1021/cr00097a009 pmid: 17849483
	(g) Mantri P.; Duffy D. E.; Kettner C. A. J. Org. Chem. 1996, 61, 5690. doi: 10.1021/jo960628l pmid: 17849483
	(h) Carmes L.; Carreaux F.; Carboni B.; Mortier J. Tetrahedron Lett. 1998, 39, 555. doi: 10.1016/S0040-4039(97)10682-7 pmid: 17849483
	(i) Lebarbier C.; Carreaux F.; Carboni B.; Boucher J. L. Bioorg. Med. Chem. Lett. 1998, 8, 2573. pmid: 17849483
	(j) Singh R. P.; Matteson D. S. J. Org. Chem. 2000, 65, 6650. pmid: 17849483
	(k) Jagannathan S.; Forsyth T. P.; Kettner C. A. J. Org. Chem. 2001, 66, 6375. pmid: 17849483
	(l) Matteson D. S. Med. Res. Rev. 2008, 28, 233. pmid: 17849483
	(m) Matteson D. S.; Maliakal D.; Fabry-Asztalos L. J. Organomet. Chem. 2008, 693, 2258. doi: 10.1016/j.jorganchem.2008.03.031 pmid: 17849483
	(n) Batsanov A. S.; Grosjean C.; Schutz T.; Whiting A. J. Org. Chem. 2007, 72, 6276. pmid: 17849483
[13]	(a) Wang Z.; Bachman S.; Dudnik A. S.; Fu G. C. Angew. Chem., Int. Ed. 2018, 57, 14529. pmid: 19653692
	(b) Cheng Q. Q.; Zhu S. F.; Zhang Y. Z.; Xie X. L.; Zhou Q. L. J. Am. Chem. Soc. 2013, 135, 14094. doi: 10.1021/ja408306a pmid: 19653692
	(c) Joannou M. V.; Moyer B. S.; Meek S. J. J. Am. Chem. Soc. 2015, 137, 6176. doi: 10.1021/jacs.5b03477 pmid: 19653692
	(d) Chen D.; Zhang X.; Qi W. Y.; Xu B.; Xu M.-H. J. Am. Chem. Soc. 2015, 137, 5268. doi: 10.1021/jacs.5b00892 pmid: 19653692
	(e) Zhan M.; Li R.-Z.; Mou Z. D.; Cao C.-G.; Liu J.; Chen Y.-W.; Niu D.-W. ACS Catal. 2016, 6, 3381. doi: 10.1021/acscatal.6b00719 pmid: 19653692
	(f) Potter B.; Szymaniak A. A.; Edelstein E. K.; Morken J. P. J. Am. Chem. Soc. 2014, 136, 17918. doi: 10.1021/ja510266x pmid: 19653692
	(g) Sun C.; Potter B.; Morken J. P. J. Am. Chem. Soc. 2014, 136, 6534. doi: 10.1021/ja500029w pmid: 19653692
	(h) Smilovic I. G.; Casas-Arce E.; Roseblade S. J.; Nettekoven U.; Zanotti-Gerosa A.; Kovacevic M.; Casar Z. Angew. Chem., Int. Ed. 2012, 51, 1014. pmid: 19653692
	(i) Chen I.-H.; Yin L.; Itano W.; Kanai M.; Shibasaki M. J. Am. Chem. Soc. 2009, 131, 11664. doi: 10.1021/ja9045839 pmid: 19653692
	(j) Sim H.-S.; Feng X.; Yun J. Chem.-Eur. J. 2009, 15, 1939. doi: 10.1002/chem.v15:8 pmid: 19653692
	(k) Kitanosono T.; Xu P.; Isshiki S.; Zhu L.; Kobayashi S. Chem. Commun. 2014, 50, 9336. doi: 10.1039/C4CC04062G pmid: 19653692
	(l) Lee J. E.; Yun J. Angew. Chem., Int. Ed. 2008, 47, 145. pmid: 19653692
	(m) Kitanosono T.; Kobayashi S. Asian J. Org. Chem. 2013, 2, 961. doi: 10.1002/ajoc.v2.11 pmid: 19653692
	(n) O'Brien, J. M.; Lee, K.-S.; Hoveyda, A. H. J. Am. Chem. Soc. 2010, 132, 10630. doi: 10.1021/ja104777u pmid: 19653692
[14]	(a) Woźniak Ł.; Tan J. F.; Nguyen Q. H.; Madron du Vigné A.; Smal V.; Cao Y. X.; Cramer N. Chem. Rev. 2020, 120, 10516. doi: 10.1021/acs.chemrev.0c00559 pmid: 32897713
	(b) Zhao M.; Song P.-D.; Jiao J.; Li P.-F. Chin. J. Chem. 2020, 38, 665. doi: 10.1002/cjoc.v38.6 pmid: 32897713
	(c) Wang X.-Y.; Zhang P.-F.; Ye M.-C. Chin. J. Chem. 2020, 38, 1762. doi: 10.1002/cjoc.v38.12 pmid: 32897713
	(d) Wang W.-F.; Sun W. Chin. J. Org. Chem. 2023, 43, 1605. (in Chinese) doi: 10.6023/cjoc202300023 pmid: 32897713
	(王文芳, 孙伟, 有机化学, 2023, 43, 1605.) doi: 10.6023/cjoc202300023 pmid: 32897713
[15]	(a) Su B.; Hartwig J. F. Angew. Chem., Int. Ed. 2022, 61, e202113343. doi: 10.1002/anie.v61.9
	(b) Tamura H.; Yamazaki H.; Sato H.; Sakaki S. J. Am. Chem. Soc. 2003, 125, 16114. doi: 10.1021/ja0302937
	(c) Boller T. M.; Murphy J. M.; Hapke M.; Ishiyama T.; Miyaura N.; Hartwig J. F. J. Am. Chem. Soc. 2005, 127, 14263. doi: 10.1021/ja053433g
[16]	Park D.; Baek D.; Lee C.-W.; Ryu H.; Park S.; Han W.; Hong S. Tetrahedron 2021, 79, 131811. doi: 10.1016/j.tet.2020.131811
[17]	Baek D.; Ryu H.; Ryu J. Y.; Lee J.; Stoltz B. M.; Hong S. Chem. Sci. 2020, 11, 4602. doi: 10.1039/D0SC00412J
[18]	Wang G.-H.; Liu L.; Wang H.; Ding Y. S.; Zhou J.; Mao S.; Li P.-F. J. Am. Chem. Soc. 2017, 139, 91. doi: 10.1021/jacs.6b11867
[19]	Zou X.-L.; Zhao H.-N.; Li Y.-W.; Gao Q.; Ke Z.-F.; Xu S.-M. J. Am. Chem. Soc. 2019, 141, 5334. doi: 10.1021/jacs.8b13756
[20]	Lemouzy S.; Giordano L.; Hérault D.; Buono G. Eur. J. Org. Chem. 2020, 2020, 3351. doi: 10.1002/ejoc.v2020.23
[21]	Song S.-Y.; Li Y.-W.; Ke Z.-F.; Xu S.-M. ACS Catal. 2021, 11, 13445. doi: 10.1021/acscatal.1c03888
[22]	Jing K.; Chen L.-L.; Zhang P.; Xu S.-M. Chin. J. Chem. 2023, 41, 2119. doi: 10.1002/cjoc.v41.17
[23]	Song S.-Y.; Zhou X.-Y.; Ke Z.-F.; Xu S.-M. Angew. Chem., Int. Ed. 2023, 62, e202217130.
[24]	(a) Kim B.; Chinn A. J.; Fandrick D. R.; Senanayake C. H.; Singer R. A.; Miller S. J. J. Am. Chem. Soc. 2016, 138, 7939. doi: 10.1021/jacs.6b03444
	(b) Metrano A. J.; Miller S. J. Acc. Chem. Res. 2019, 52, 199. doi: 10.1021/acs.accounts.8b00473
[25]	Genov G. R.; Douthwaite J. L.; Lahdenperä A. S. K.; Gibson D. C.; Phipps R. J. Science 2020, 367, 1246. doi: 10.1126/science.aba1120
[26]	Song P.-D.; Hu L.-L.; Yu T.; Jiao J.; He Y.-Q.; Xu L.; Li P.-F. ACS Catal. 2021, 11, 7339. doi: 10.1021/acscatal.1c01671
[27]	(a) Fu G. C. Acc. Chem. Res. 2006, 39, 853. doi: 10.1021/ar068115g
	(b) Rios R.; Liang J.; Lo M. M. C.; Fu G. C. Chem. Commun. 2000, 377.
[28]	Lötscher D.; Rupprecht S.; Stoeckli-Evans H.; von Zelewsky A. Tetrahedron: Asymmetry 2000, 11, 4341. doi: 10.1016/S0957-4166(00)00401-8
[29]	(a) Fu G. C. Acc. Chem. Res. 2004, 37, 542. doi: 10.1021/ar030051b
	(b) Fu G. C. Acc. Chem. Res. 2000, 33, 412. doi: 10.1021/ar990077w
	(c) Gomez Arrayas R.; Adrio J.; Carretero J. C. Angew. Chem., Int. Ed. 2006, 45, 7674. doi: 10.1002/(ISSN)1521-3773
	(d) Dai L.-X.; Tu T.; You S.-L.; Deng W.-P.; Hou X.-L. Acc. Chem. Res. 2003, 36, 659. doi: 10.1021/ar020153m
[30]	Zou X.-L.; Li Y.-W.; Ke Z.-F.; Xu S.-M. ACS Catal. 2022, 12, 1830. doi: 10.1021/acscatal.1c05299
[31]	(a) Newton C. G.; Wang S. G.; Oliveira C. C.; Cramer N. Chem. Rev. 2017, 117, 8908. doi: 10.1021/acs.chemrev.6b00692
	(b) Saint-Denis T. G.; Zhu R.-Y.; Chen G.; Wu Q.-F.; Yu J.-Q. Science 2018, 359, eaao4798. doi: 10.1126/science.aao4798
[32]	(a) He J.; Jiang H.; Takise R.; Zhu R.-Y.; Chen G.; Dai H.-X.; Dhar T. G. M.; Shi J.; Zhang H.; Cheng P. T.; Yu J.-Q. Angew. Chem., Int. Ed. 2016, 55, 785.
	(b) Zhang L.-S.; Chen G.-H.; Wang X.; Guo Q.-Y.; Zhang X.-S.; Pan F.; Chen K.; Shi Z.-J. Angew. Chem., Int. Ed. 2014, 53, 3899. doi: 10.1002/anie.201310000
[33]	He J.; Shao Q.; Wu Q.-F.; Yu J.-Q., J. J. Am. Chem. Soc. 2017, 139, 3344. doi: 10.1021/jacs.6b13389
[34]	Chen X.; Chen L.-L.; Zhao H.-L.; Gao Q.; Shen Z.-L.; Xu S.-M. Chin. J. Chem. 2020, 38, 1533. doi: 10.1002/cjoc.v38.12
[35]	Ebner C.; Carreira E. M. Chem. Rev. 2017, 117, 11651. doi: 10.1021/acs.chemrev.6b00798
[36]	(a) Gagnon A.; Duplessis M.; Fader L. Org. Prep. Proced. Int. 2010, 42, 1. doi: 10.1080/00304940903507788
	(b) Talele T. T. J. Med. Chem. 2016, 59, 8712. doi: 10.1021/acs.jmedchem.6b00472
[37]	Wu W.-Q.; Lin Z.-M.; Jiang H.-F. Org. Biomol. Chem. 2018, 16, 7315. doi: 10.1039/C8OB01187G
[38]	Shi Y.-J.; Yang Y.-H.; Xu S.-M. Angew. Chem., Int. Ed. 2022, 61, e202201463.
[39]	Gao Q.; Xu S.-M. Angew. Chem., Int. Ed. 2023, 62, e202218025. doi: 10.1002/anie.v62.8
[40]	Chen L.-L.; Yang Y.-H.; Liu L.-H.; Gao Q.; Xu S.-M. J. Am. Chem. Soc. 2020, 142, 12062. doi: 10.1021/jacs.0c06756
[41]	Giri R.; Shi B.-F.; Engle K. M.; Maugel N.; Yu J.-Q. Chem. Soc. Rev. 2009, 38, 3242. doi: 10.1039/b816707a
[42]	(a) Kang E.; Kim H. T.; Joo J. M. Org. Biomol. Chem. 2020, 18, 6192. doi: 10.1039/D0OB01265C
	(b) Lee W.-G. C.; Shen Y.; Gutierrez D. A.; Li J. J. Org. Lett. 2016, 18, 2660. doi: 10.1021/acs.orglett.6b01105
	(c) Shen Y.; Lee W.-G. C.; Gutierrez D. A.; Li J. J. J. Org. Chem. 2017, 82, 11620. doi: 10.1021/acs.joc.7b01883
	(d) Yuan C.; Tu G.; Zhao Y. Org. Lett. 2017, 19, 356.
	(e) Kim H.; Thombal R. S.; Khanal H. D.; Lee Y. R. Chem. Commun. 2019, 55, 13402. doi: 10.1039/C9CC06758B
[43]	Kashima C.; Hibi S.; Maruyama T.; Harada K.; Omote Y. J. Heterocycl. Chem. 1987, 24, 637. doi: 10.1002/jhet.v24:3
[44]	Du R.-R.; Liu L.-H.; Xu S.-M. Angew. Chem., Int. Ed. 2021, 60, 5843. doi: 10.1002/anie.v60.11
[45]	Yang Y.-H.; Chen L.-L.; Xu S.-M. Angew. Chem., Int. Ed. 2021, 60, 3524. doi: 10.1002/anie.v60.7
[46]	Chen X.; Cheng Z.-Y.; Guo J.; Lu Z. Nat. Commun. 2018, 9, 3939. doi: 10.1038/s41467-018-06240-y pmid: 30258070
[47]	Zhang M.-H.; Ye Z.-Y.; Zhao W.-X. Angew. Chem., Int. Ed. 2023, 62, e202306248. doi: 10.1002/anie.v62.31

过渡金属催化不对称C—H硼化反应研究进展