Stereospecific Nickel-Catalyzed Borylation of Secondary Benzyl Pivalates

R. Martin-Montero; T. Krolikowski; C. Zarate; R. Manzano; R. Martin

doi:10.1055/s-0036-1590962

Synlett, Table of Contents

Synlett 2017; 28(19): 2604-2608
DOI: 10.1055/s-0036-1590962

cluster

Stereospecific Nickel-Catalyzed Borylation of Secondary Benzyl Pivalates

R. Martin-Montero

^aInstitute of Chemical Research of Catalonia (ICIQ), Av. Paisos Catalans 16, 43007, Tarragona, Spain Email: rmartinromo@iciq.es

,

T. Krolikowski

^aInstitute of Chemical Research of Catalonia (ICIQ), Av. Paisos Catalans 16, 43007, Tarragona, Spain Email: rmartinromo@iciq.es

,

C. Zarate

^aInstitute of Chemical Research of Catalonia (ICIQ), Av. Paisos Catalans 16, 43007, Tarragona, Spain Email: rmartinromo@iciq.es

,

R. Manzano

^aInstitute of Chemical Research of Catalonia (ICIQ), Av. Paisos Catalans 16, 43007, Tarragona, Spain Email: rmartinromo@iciq.es

,

R. Martin*

^aInstitute of Chemical Research of Catalonia (ICIQ), Av. Paisos Catalans 16, 43007, Tarragona, Spain Email: rmartinromo@iciq.es

^bCatalan Institution for Research and Advanced Studies (ICREA), Passseig Lluis Companys, 23, 08010, Barcelona, Spain

› Author Affiliations

Abstract

All articles of this category

Published as part of the Cluster C–O Activation

Abstract

A stereoselective nickel-catalyzed direct borylation of enantioenriched secondary benzyl pivalates is described. This methodology is characterized by an intriguing cooperativity of simple nickel and copper salts to promote the targeted C–B bond formation under mild reaction conditions. Unlike classical S_N2-type processes, this protocol occurs with a neat retention of configuration, resulting in synthetically versatile benzyl boronic esters with excellent stereochemical fidelity.

Key words

borylation - nickel - cooperativity - stereoselective - C–O bonds

Full Text

References

References and Notes

1a Zarate C. Van Gemmeren M. Somerville RJ. Martin R. Adv. Organomet. Chem. 2016; 66: 143
1b Tollefson EJ. Hanna LE. Jarvo ER. Acc. Chem. Res. 2015; 47: 2344
1c Su B. Cao Z.-C. Shi Z.-J. Acc. Chem. Res. 2015; 48: 886
1d Tobisu M. Chatani N. Acc. Chem. Res. 2015; 48: 1717
1e Cornella J. Zarate C. Martin R. Chem. Soc. Rev. 2014; 43: 8081
1f Yamaguchi J. Muto K. Itami K. Eur. J. Org. Chem. 2013; 19
1g Rosen BM. Quasdorf KW. Wilson DA. Zhang N. Resmerita A.-M. Garg N. Percec V. Chem. Rev. 2011; 111: 1346

For selected enantioselective, rather than stereospecific, cross-coupling reactions of C–O electrophiles other than particularly activated organic sulfonates, see:

2a Cornella J. Jackson EP. Martin R. Angew. Chem. Int. Ed. 2015; 54: 4075
2b Oelke AJ. Jianwei S. Fu GC. J. Am. Chem. Soc. 2012; 134: 2966

3 Chenery AH. Kadunce NT. Reisman SE. Chem. Rev. 2015; 115: 9587
4 Eliel EL. Wilen SH. Stereochemistry of Organic Compounds . John Wiley and Sons; New York: 1994

5a Erickson LW. Lucas EL. Tollefson EJ. Jarvo ER. J. Am. Chem. Soc. 2016; 138: 14006
5b Konev MO. Hanna LE. Jarvo ER. Angew. Chem. Int. Ed. 2016; 55: 6730
5c Tollefson EJ. Dawson DD. Osborne CA. Jarvo ER. J. Am. Chem. Soc. 2014; 136: 14951
5d Harris MR. Konev MO. Jarvo ER. J. Am. Chem. Soc. 2014; 136: 7825
5e Yonova IM. Johnson AG. Osborne CA. Moore CE. Morrissette NS. Jarvo ER. Angew. Chem. Int. Ed. 2014; 53: 2422
5f Harris MR. Hanna LE. Greene MA. Moore CE. Jarvo ER. J. Am. Chem. Soc. 2013; 135: 3303
5g Taylor BL. H. Swift EC. Waetzig JD. Jarvo ER. J. Am. Chem. Soc. 2011; 133: 389

6a Zhou Q. Cobb KM. Tan T. Watson MP. J. Am. Chem. Soc. 2016; 138: 12057
6b Zhou Q. Srnivas HD. Zhang S. Watson MP. J. Am. Chem. Soc. 2016; 138: 11989
6c Srnivas HD. Zhou Q. Watson MP. Org. Lett. 2014; 16: 3596
6d Zhou Q. Srinivas HD. Dasgupta S. Watson MP. J. Am. Chem. Soc. 2013; 135: 3307

For selected references, see:

7a Zarate C. Nakajima M. Martin R. J. Am. Chem. Soc. 2017; 139: 1191
7b Zarate C. Manzano R. Martin R. J. Am. Chem. Soc. 2015; 137: 6754
7c Zarate CM. Martin R. J. Am. Chem. Soc. 2014; 136: 7253
7d Tobisu M. Yasutome A. Yamakawa A. Yamakawa K. Shimasaki T. Chatani N. Tetrahedron 2012; 68: 5157
7e Tobisu M. Shimasaki T. Chatani N. Chem. Lett. 2009; 38: 710

For selected comprehensive reviews on C–heteroatom bond-forming reactions:

8a Zhu X. Chiba S. Chem. Soc. Rev. 2016; 45: 4504
8b Surry DS. Buchwald SL. Chem. Sci. 2011; 2: 27
8c Catalyzed Carbon-Heteroatom Bond-Formation . Yudin AK. Wiley-VCH; Weinheim: 2010
8d Hartwig JF. Nature 2008; 455: 314

9 Tobisu M. Zhao J. Kinuta H. Furukawa T. Igarashi T. Chatani N. Adv. Synth. Catal. 2016; 358: 2417

Selected references:

10a ref. 2a and 7a,b.
10b Gu Y. Martin R. Angew. Chem. Int. Ed. 2017; 56: 3187
10c Correa A. Martin R. J. Am. Chem. Soc. 2014; 136: 7253
10d Correa A. León T. Martin R. J. Am. Chem. Soc. 2014; 136: 1062
10e Alvarez-Bercedo P. Martin R. J. Am. Chem. Soc. 2010; 132: 17352
10f Cornella J. Martin R. Org. Lett. 2013; 15: 6298
10g Cornella J. Gómez-Bengoa E. Martin R. J. Am. Chem. Soc. 2013; 135: 1997

11a Sandford C. Aggarwal VK. Chem. Commun. 2017; 53: 5481
11b Hall DG. Boronic Acids . Wiley-VCH; Weinheim: 2005

12 For details, see Supporting Information.
13 The mass balance of the reaction accounts for the formation of 2-ethylnaphthalene via protodeborylation and the corresponding homobenzylboronic ester obtained from the putative oxidative addition species by a β-hydride elimination/migratory insertion prior C–B bond formation at the terminal position.
14 The synergistic use of CuF₂ and low-valent nickel species was initially demonstrated by our group when forging C–Si bonds, see ref. 7c. For the beneficial role of CsF in recent C–O bond-cleavage procedures, see: Schwarzer MC. Konno R. Hojo T. Ohtsuki A. Nakamura K. Yasutome A. Takahashi H. Shimasaki T. Tobisu M. Chatani N. Mori S. J. Am. Chem. Soc. 2017; 139: 10347

For recent examples of Ni/Cu cooperativity for effecting C–heteroatom bond-forming reactions, see:

15a Gou L. Chatupheeraphat A. Rueping M. Angew. Chem. Int. Ed. 2016; 55: 11810
15b Semba K. Ohtagaki Y. Nakao Y. Org. Lett. 2016; 18: 3956
15c Pu X. Hu J. Zhao Y. Shi Z. ACS Catal. 2016; 6: 6692

16 Bakshi RK. Shibata S. Chen C. Singh VK. Corey EJ. J. Am. Chem. Soc. 1987; 109: 7925
17 Recovered starting material was observed when employing non-π-extended aryl pivalates.

18a Netherton MR. Fu GC. Angew. Chem. Int. Ed. 2002; 41: 3910
18b Stille JK. In The Chemistry of the Metal–Carbon Bond . Vol. 2. Hartley FR. Patai S. John Wiley and Sons; New York: 1985: 625

For selected references limited to π-extended systems or to the presence of ortho- or para-activating groups, see:

19a Guo L. Liu X. Baumann C. Rueping M. Angew. Chem. Int. Ed. 2016; 55: 15415
19b Zhao Y. Snieckus V. J. Am. Chem. Soc. 2014; 136: 11224
19c Yu D.-G. Shi Z.-J. Angew. Chem. Int. Ed. 2011; 50: 7097
19d Tobisu M. Yamakawa K. Shimasaki T. Chatani N. Chem. Commun. 2011; 47: 2946
19e Yu DG. Li BJ. Zheng SF. Guan BT. Wang BQ. Shi ZJ. Angew. Chem. Int. Ed. 2010; 49: 4566
19f Alvarez-Bercedo R. Martin R. J. Am. Chem. Soc. 2010; 132: 17352
19g Tobisu M. Shimasaki T. Chatani N. Angew. Chem. Int. Ed. 2008; 47: 4866

20 η²-Coordination of π-extended systems to low-valent metal complexes is known to be stronger than regular arenes due to the partial preservation of the aromaticity: Bauer DJ. Krueger C. Inorg. Chem. 1977; 16: 884
21 Martin R. Buchwald SL. Acc. Chem. Res. 2008; 41: 1461
22 Imao D. Glasspole BW. Laberge VS. Crudden CM. J. Am. Chem. Soc. 1987; 109: 4756

23a Zweifel G. Arzoumanian H. Whitney CC. J. Am. Chem. Soc. 1967; 89: 3652
23b Evans A. Crawford TC. Thomas RC. Walker JA. J. Org. Chem. 1976; 41: 3947
23c Sonawane RP. Jheengut V. Rabalakos C. Larouche-Gauthier R. Scott HK. Aggarwal VK. Angew. Chem. Int. Ed. 2011; 50: 3760

24 (R)-1-(6-fluoronaphthalen-2-yl)ethanol (2d) – Typical ProcedureA 5 mL oven-dried screw-capped test tube containing a stirring bar was charged with the benzyl pivalate 1d (54.8 mg, 0.2 mmol). The test tube was introduced in an argon-filled glovebox where B₂nep₂ (67.8 mg, 0.3 mmol, 1.5 equiv), CuF₂ (6 mg, 30 mol%), CsF (9.1 mg, 30 mol%), Ni(COD)₂ (304 μL, 7.5 mol%, 0.05 M in toluene), PCy₃ (152 μL, 7.5 mol%, 0.1 M), and toluene (1 mL) were then added sequentially. The tube with the mixture was taken out of the glovebox and stirred at 50 °C for 15 h. The mixture was then allowed to warm to room temperature, diluted with EtOAc (5 mL), and filtered through a Celite^® plug, eluting with additional EtOAc (5mL). The filtrate was concentrated removing the volatiles. Then the reaction was cooled to 0 °C (water/ice bath) and BHT (ca. 1 mg) was added followed by anhydrous THF (1 mL). An ice-cold degassed mixture of 3 M NaOH (1.2 mL) and 30% aq H₂O₂ (0.75 mL) was added all at once. The reaction mixture was stirred at room temperature for 2 h. Then, the reaction mixture was diluted with water (4 mL) and extracted with Et₂O (3 × 10 mL). The combined organic layers were washed with brine and dried over MgSO₄. The filtrate was concentrated and purified by silica gel chromatography to give the title product 2d (30.5 mg, 80%) as a white solid (mp 84–86 °C). The enantiomeric excess was determined to be 65% ee (88% ee_s) by chiral HPLC analysis (CHIRALPAK IB, 1 mL/min, 2% EtOH/hexane, λ = 220 nm): t _R (minor) = 12.4 min, t _R (major) = 13.9 min. [α]_D ²⁴ = 43.2 (c 0.06, CHCl₃).¹H NMR (500 MHz, CDCl₃): δ = 7.83–7.76 (m, 3 H), 7.53 (dd, J = 2.0 Hz, 1 H), 7.44 (dd, J = 2.6 Hz, 1 H), 7.26 (td, J = 2.6 Hz, 1 H), 5.06 (q, J = 6.4 Hz, 1 H), 1.97 (s, 1 H, OH), 1.58 (d, J = 6.4 Hz, 3 H) ppm. ¹³C NMR (126 MHz, CDCl₃): δ = 161.8, 159.4, 142.5, 133.6, 130.3, 127.7, 124.9, 123.8, 116.6, 110.7, 70.3, 25.2 ppm. ¹⁹F NMR (376 MHz, CDCl₃): δ = –115.1 ppm.

Supplementary Material

Supporting Information