Synlett 2014; 25(08): 1132-1136
DOI: 10.1055/s-0033-1341048
letter
© Georg Thieme Verlag Stuttgart · New York

Iron-Catalyzed Borylation Reactions of Alkynes: An Efficient Synthesis of E-Vinyl Boronates

Vikas S. Rawat
Inorganic & Physical Chemistry Division, Indian Institute of Chemical Technology (Council of Scientific & Industrial Research), Hyderabad 500607, India   Fax: +91(40)27160921   Email: sreedharb@iict.res.in
,
Bojja Sreedhar*
Inorganic & Physical Chemistry Division, Indian Institute of Chemical Technology (Council of Scientific & Industrial Research), Hyderabad 500607, India   Fax: +91(40)27160921   Email: sreedharb@iict.res.in
› Author Affiliations
Further Information

Publication History

Received: 23 December 2013

Accepted after revision: 02 March 2014

Publication Date:
27 March 2014 (online)


Abstract

Iron nanoparticles or ferric chloride catalyze the monoborylation of alkynes using bis(pinacolato)diboron to provide E-vinyl boronates with high regio- and stereoselectivity in good to excellent yields. High catalytic activity was observed and the catalyst could be recovered simply by using an external magnetic field. The magnetic nanoparticles were recycled six times without any significant loss of catalytic activity.

Supporting Information

 
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  • 19 Typical Procedure: A mixture of alkyne (1 mmol), bis(pinacolato)diboron (1.2 mmol), Cs2CO3 (2 mmol) and np Fe3O4 or FeCl3 (5 mol%) in acetone (5 mL) in a sealed tube was heated at 60 °C for 12 h. After completion of the reaction, EtOAc (1 mL) was added to the reaction mixture. An external magnet was applied to the reaction vial to accumulate catalyst, then the organic layer was decanted. This procedure was repeated two more times with EtOAc then twice with H2O. The separated catalyst was then dried in an oven. For subsequent runs, fresh starting materials were added to the vial and the reaction was conducted as described above. The combined organic and aqueous phases were separated, and the aqueous layer was extracted with EtOAc twice more. The combined organic layers were washed with brine, dried over anhydrous Na2SO4, filtered, and concentrated in vacuo. The crude product was purified by silica chromatography, eluting with hexane and acetone, to afford the pure product.
  • 20 (E)-2-[2-(6-Methoxynaphthalen-2-yl)vinyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3c): White crystalline powder; IR (KBr): 473, 633, 814, 845, 895, 973, 1000, 1033, 1144, 1164, 1203, 1262, 1330, 1357, 1392, 1460, 1482, 1502, 1620, 2932, 2976, 3052, 3428 cm–1. 1H NMR (300 MHz, CDCl3): δ = 1.32 (s, 12 H, 4CH3), 3.91 (s, 3 H, ArOCH3), 6.22 (d, J = 18.1 Hz, 1 H, trans-CH=CH), 7.08–7.13 (m, 2 H, ArH), 7.51–7.56 (m, 1 H, ArH), 7.64–7.23 (m, 3 H, ArH), 7.77 (s, 1 H, ArH). 13C NMR (75 MHz, CDCl3): δ = 24.7, 55.3, 83.2, 105.7, 118.4, 118.9, 123.9, 125.5, 126.5, 127.0, 127.8, 129.8, 134.9, 149.6, 158.1. MS (ESI): m/z = 311 [M]+. HRMS (ESI+): m/z [M]+ calcd for C19H24O3B: 311.1813; found: 311.1820.
  • 21 (E)-2-[3,5-Bis(trifluoromethyl)styryl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3d): Light-yellow oil; IR (neat): 682, 705, 724, 846, 896, 968, 1137, 1174, 1279, 1332, 1377, 1464, 1513, 1624, 1716, 2856, 2928 cm–1. 1H NMR (300 MHz, CDCl3): δ = 1.31 (s, 12 H, 4CH3), 6.31 (d, J = 17.9 Hz, 1 H, trans-CH=CH), 7.41 (d, J = 18.9 Hz, 1 H, trans-CH=CH), 7.77 (s, 1 H, ArH), 7.88 (s, 2 H, ArH). 13C NMR (75 MHz, CDCl3): δ = 24.7, 83.4, 119.5, 126.3, 126.7, 128.4, 131.0, 136.7, 145.8. MS (ESI): m/z = 391 [M + Na]+. HRMS (ESI+): m/z [M + H]+ calcd for C16H18BF6O2: 367.1299; found: 367.1298.