a and Tarun K. Panda*a Table of contents · Adimulam Harinath,a Indrani Banerjee,a Jayeeta...

Supporting Information for

Aluminium complex–catalysed hydroboration of alkenes and

alkynes

Adimulam Harinath,a Indrani Banerjee,a Jayeeta Bhattacharjeea and Tarun K. Panda*a

Table of contents

Table TS1. Crystallographic data and refinement parameters of 1.

FS1.1H NMR spectrum (400 MHz, 25°C, C6D6) of complex 1.

FS2.11B NMR spectrum (128.4 MHz, 25°C, C6D6) of complex 1.

FS3.13C NMR spectrum (100 MHz, 25°C, C6D6) of complex 1.

FS4.1H NMR spectrum (400 MHz, 25°C, CDCl3) of 2a.

FS5.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of 2a.

FS6.13C NMR spectrum (100 MHz, 25°C, CDCl3) of 2a.

FS7.1H NMR spectrum (400 MHz, 25°C, CDCl3) of 2b.

FS8.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of 2b.

FS9.13C NMR spectrum (100 MHz, 25°C, CDCl3) of 2b.

FS10.1H NMR spectrum (400 MHz, 25°C, CDCl3) of 2c.

FS11.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of 2c.

FS12.13C NMR spectrum (100 MHz, 25°C, CDCl3) of 2c.

FS13.1H NMR spectrum (400 MHz, 25°C, CDCl3) of 2d.

FS14.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of 2d.

FS15.13C NMR spectrum (100 MHz, 25°C, CDCl3) of 2d.

FS16.1H NMR spectrum (400 MHz, 25°C, CDCl3) of 2e.

FS17.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of 2e.

FS18.13C NMR spectrum (100 MHz, 25°C, CDCl3) of 2e.

FS19.1H NMR spectrum (400 MHz, 25°C, CDCl3) of 2f.

FS20.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of 2f.

FS21.13C NMR spectrum (100 MHz, 25°C, CDCl3) of 2f.

Electronic Supplementary Material (ESI) for New Journal of Chemistry.This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2019

FS22.1H NMR spectrum (400 MHz, 25°C, CDCl3) of 2g.

FS23.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of 2g.

FS24. 19F NMR spectrum (376.5 MHz, 25°C, CDCl3) of 2g.

FS25.13C NMR spectrum (100 MHz, 25°C, CDCl3) of 2g.

FS26.1H NMR spectrum (400 MHz, 25°C, CDCl3) of 2h.

FS27.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of 2h.

FS28.13C NMR spectrum (100 MHz, 25°C, CDCl3) of 2h.

FS29.1H NMR spectrum (400 MHz, 25°C, CDCl3) of 2i.

FS30.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of 2i.

FS31.13C NMR spectrum (100 MHz, 25°C, CDCl3) of 2i.

FS32.1H NMR spectrum (400 MHz, 25°C, CDCl3) of 2j.

FS33.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of 2j.

FS34.13C NMR spectrum (100 MHz, 25°C, CDCl3 of 2j.

FS35.1H NMR spectrum (400 MHz, 25°C, CDCl3) of 2k.

FS36.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of 2k.

FS37.13C NMR spectrum (100 MHz, 25°C, CDCl3 of 2k.

FS38.1H NMR spectrum (400 MHz, 25°C, CDCl3) of 2l.

FS39.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of 2l.

FS40.13C NMR spectrum (100 MHz, 25°C, CDCl3 of 2l.

FS41.1H NMR spectrum (400 MHz, 25°C, CDCl3) of 2m.

FS42.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of 2m.

FS43.13C NMR spectrum (100 MHz, 25°C, CDCl3 of 2m.

FS44.1H NMR spectrum (400 MHz, 25°C, CDCl3) of 2n.

FS45.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of 2n.

FS46.13C NMR spectrum (100 MHz, 25°C, CDCl3 of 2n.

FS47.1H NMR spectrum (400 MHz, 25°C, CDCl3) of 2o.

FS48.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of 2o.

FS49.13C NMR spectrum (100 MHz, 25°C, CDCl3 of 2o.

FS50.1H NMR spectrum (400 MHz, 25°C, CDCl3) of 2p.

FS51.11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of 2p.

FS52.13C NMR spectrum (100 MHz, 25°C, CDCl3 of 2p.


FS54. 11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of 3a.

FS55.13C NMR spectrum (100 MHz, 25°C, CDCl3 of 3a.

FS56.1H NMR spectrum (400 MHz, 25°C, CDCl3) of 3b.

FS57. 11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of 3b.

FS58.13C NMR spectrum (100 MHz, 25°C, CDCl3 of 3b.

FS59.1H NMR spectrum (400 MHz, 25°C, CDCl3) of 3c.

FS60. 11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of 3c.

FS61.13C NMR spectrum (100 MHz, 25°C, CDCl3 of 3c.

FS62.1H NMR spectrum (400 MHz, 25°C, CDCl3) of 3d.

FS63. 11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of 3d.

FS64.13C NMR spectrum (100 MHz, 25°C, CDCl3 of 3d.

FS65.1H NMR spectrum (400 MHz, 25°C, CDCl3) of 3e.

FS66. 11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of 3e.

FS67.13C NMR spectrum (100 MHz, 25°C, CDCl3 of 3e.

FS68.1H NMR spectrum (400 MHz, 25°C, CDCl3) of 3f.

FS69. 11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of 3f.

FS70.13C NMR spectrum (100 MHz, 25°C, CDCl3 of 3f.

FS71.1H NMR spectrum (400 MHz, 25°C, CDCl3) of 3g.

FS72. 11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of 3g.

FS73.13C NMR spectrum (100 MHz, 25°C, CDCl3 of 3g.

FS74.1H NMR spectrum (400 MHz, 25°C, CDCl3) of 3h.

FS75. 11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of 3h.

FS76.13C NMR spectrum (100 MHz, 25°C, CDCl3 of 3h.

FS77.1H NMR spectrum (400 MHz, 25°C, CDCl3) of 3i.

FS78. 11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of 3i.

FS79.13C NMR spectrum (100 MHz, 25°C, CDCl3 of 3i.

FS80.1H NMR spectrum (400 MHz, 25°C, CDCl3) of 3j.

FS81. 11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of 3j.

FS82.13C NMR spectrum (100 MHz, 25°C, CDCl3 of 3j.

FS83.1H NMR spectrum (400 MHz, 25°C, CDCl3) of 3k.

FS84. 11B NMR spectrum (128.4 MHz, 25°C, CDCl3) of 3k.

FS85.13C NMR spectrum (100 MHz, 25°C, CDCl3 of 3k.


FS87.13C NMR spectrum (100 MHz, 25°C, CDCl3 of 4a.

FS88.1H NMR spectrum (100 MHz, 25°C, CDCl3 of 4b.

FS89.13C NMR spectrum (100 MHz, 25°C, CDCl3 of 4b.

Table TS1. Crystallographic data and refinement parameters of 1.

Crystal Parameters 1 (exp-6202)

CCDC No. 1909428Empirical formula C20H22N2PSeAl

Formula weight 427.30T (K) 150(2) Kλ (Å) 1.54184 Crystal system MonoclinicSpace group P 21/na (Å) 9.5906(10) b (Å) 13.1698(2) c (Å) 16.0726(2) 90 103.371(2) 90

V (Å3) 1975.04(5)Z 4Dcalc g cm-3 1.437µ (mm-1) 3.799F(000) 872Theta range for data collection

4.389 to 71.407 deg

Limiting indices -

-11 ≤ h ≤ 11, -14 ≤ k ≤ 16, -16 ≤ l ≤ 19

Reflections collected / unique

7011/ 3573 [R(int) = 0.0177]

Completeness to theta 99.7 %

Absorption correction Multi-scan

Figure FS1. 1H NMR spectrum (400 MHz, 25°C, C6D6) of complex 1.

Max. and min. transmission 1.00000 and 0.54170

Refinement method Full-matrix least-squares on F^2

Data / restraints / parameters

3753 / 0 / 229

Goodness-of-fit on F2 1.037

Final R indices [I>2sigma(I)]

R1 = 0.0311wR2 = 0.0840

R indices (all data) R1 = 0.0331 wR2 = 0.0858

Largest diff. peak and hole 0.361 and -0.553 e.Å-3

N

P

PhPhN

AlH3C CH3

Se

Figure FS2. 31P{1H} NMR spectrum (161.9 MHz, 25°C, C6D6) of complex 1.

Figure FS3 13C{1H} NMR spectrum (100 MHz, 25°C, C6D6) of complex 1.

N

P

PhPhN

AlH3C CH3

Se

N

P

PhPhN

AlH3C CH3

Se

General procedure for the synthesis of compounds (2a-2s and 3a-3m).

Catalyst 1 (1 mol%), alkenes (2a-2p) or alkynes (3a-3k) 0.5 mmol and respective boranes such

as pinacolborane/ catecholborane (0.6 mmol) were placed in a 25 mL Schlenk flask equipped

with a magnetic stir bar inside the glove box. Then the reaction mixture was stirred at 30°C for

eight hours The progress of reaction was monitored by 1H NMR spectroscopy using

hexamethylbenzene (10 mol%) as an internal standard. After the reaction was completed, the

resulted boronate ester product was separated by silica-gel column chromatography using hexane

as an eluent. Removal of solvent under reduced pressure provided pure products for further

analysis. For alkynes hydroboration was carried out in 0.5 ml toluene.

Characterization Data

4,4,5,5-tetramethyl-2-phenethyl-1,3,2-dioxaborolane (2a). 1

B O

O

Yield: [Mass in 232.13 mg (100%), Mass out 227.48 mg (98%)]. 1H NMR (400 MHz, CDCl3):

δH 7.26 - 7.20 (m, 4H, Ar-H), 7.16 - 7.11 (m, 1H, Ar-H), 2.74 (t, J = 8.0 Hz, 2H, CH2), 1.21 (s,

12H, CH3), 1.14 (t, J = 8.0 Hz, 2H, CH2) ppm. 13C{1H} NMR (100 MHz, CDCl3): δC 144.3,

128.1, 127.9, 125.4, 83.0, 29.9, 24.7 ppm. 11B{1H} NMR (128 MHz, CDCl3): δB 33.8 ppm

4,4,5,5-tetramethyl-2-(4-methylphenethyl)-1,3,2-dioxaborolane (2b). 1

B O

O


δH 7.15 (d, J = 8.0 Hz, 2H, Ar-H), 7.11 (d, J = 8.0 Hz, 2H, Ar-H), 2.76 (t, J = 8.0 Hz, 2H, CH2),

2.35 (s, 3H, CH3), 1.27 (s, 12H, CH3), 1.17 (t, J = 8.0 Hz, 2H, CH2) ppm. 13C{1H} NMR (100

MHz, CDCl3): δC 141.3, 134.7, 128.8, 127.8, 83.0, 29.4, 24.7, 20.9 ppm. 11B{1H} NMR (128

MHz, CDCl3): δB 34.0 ppm

2-(4-methoxyphenethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2c). 1

B O

O

MeO


δH 7.15 (d, J = 8.0 Hz, 2H, Ar-H), 6.82 (d, J = 8.0 Hz, 2H, Ar-H), 3.78 (s, 3H, CH3), 2.71 (t, J =

8.0 Hz, 2H, CH2), 1.23 (s, 12H, CH3), 1.13 (t, J = 8.0 Hz, 2H, CH2) ppm. 13C{1H} NMR (100

MHz, CDCl3): δC 157.5, 136.4, 128.8, 113.5, 82.9, 55.1, 29.0, 24.7 ppm. 11B{1H} NMR (128

MHz, CDCl3): δB 33.9 ppm.

2-(4-(tert-butyl)phenethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2d). 2

B O

O



1.34 (s, 9H, C(CH3)3), 1.26 (s, 12H, CH3), 1.18 (t, J = 8.0 Hz, 2H, CH2) ppm. 13C{1H} NMR

(100 MHz, CDCl3): δC 148.1, 141.3, 127.6, 125.0, 83.0, 34.2, 31.4, 29.3, 24.7 ppm. 11B{1H}

NMR (128 MHz, CDCl3): δB 34.1 ppm.

2-(4-fluorophenethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2d). 2

B O

O

F


δH 7.18 - 7.15 (m, 2H, Ar-H), 6.94 (t, J = 8.0 Hz, 2H, Ar-H), 2.72 (t, J = 8.0 Hz, 2H, CH2), 1.21

(s, 12H, CH3), 1.12 (t, J = 8.0 Hz, 2H, CH2) ppm. 13C{1H} NMR (100 MHz, CDCl3): δC 162.3,

159.8, 139.9, 129.3 (d, J = 7.0 Hz), 114.8 (d, J = 20.0 Hz), 83.1, 29.1, 24.7 ppm. 11B{1H} NMR

(128 MHz, CDCl3): δB 33.5 ppm

2-(4-Bromophenethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2e). 3

B O

O

Br



1.22 (s, 12H, CH3), 1.11 (t, J = 8.0 Hz, 2H, CH2) ppm. 13C{1H} NMR (100 MHz, CDCl3): δC

143.3, 131.1, 129.8, 119.1, 83.1, 29.3, 24.7 ppm. 11B{1H} NMR (128 MHz, CDCl3): δB 34.0

ppm.

4,4,5,5-tetramethyl-2-(2-(perfluorophenyl)ethyl)-1,3,2-dioxaborolane (2f). 1

B O

O

F

FF

FF


δH 2.80 - 2.75 (m, 2H, CH2), 1.22 (s, 12H, CH3), 1.11 - 1.06 (m, 2H, CH2) ppm. 13C{1H} NMR

(100 MHz, CDCl3): δC 146.2 - 146.0 (m, CF), 143.7-143.6 (m, CF), 140.5 - 140.4 (m, CF), 138.5

- 138.0 (m, CF), 127.3 - 116.9 (m, CF), 83.4, 24.7, 16.9 ppm. 11B{1H} NMR (128 MHz, CDCl3):

δB 33.2 ppm

2-(3-cyclohexylpropyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

B O

O

Yield: [Mass in 252.20 mg (100%), Mass out 214.37 mg (85%)] : δH 1.69 - 1.63 (m, 6H, CH2),

1.41 - 1.37 (m, 2H, CH2), 1.22 (s, 12H, CH3), 1.17 - 1.12 (m, 5H, CH2), 0.88 - 0.81 (m, 2H,

CH2), 0.72 (t, J = 8.0 Hz, 2H, CH2) ppm. 13C{1H} NMR (100 MHz, CDCl3): δC 82.7, 40.4, 37.4,

33.3, 26.7, 26.4, 24.7, 21.2 ppm. 11B{1H} NMR (128 MHz, CDCl3): δB 34.1 ppm.

2-(2-cyclohexylethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(2h). 2

B O

O

Yield: [Mass in 238.17 mg (100%), Mass out 197.68 mg (83%)]: δH 1.69 - 1.59 (m, 4H, CH2),

1.43 - 1.35 (m, 1H, CH), 1.22 (s, 12H, CH3), 1.17 - 1.12 (m, 4H, CH2), 0.88 - 0.81 (m, 2H, CH2),

0.72 (t, J = 8.0 Hz, 2H, CH2) ppm. 13C{1H} NMR (100 MHz, CDCl3): δC 82.7, 40.4, 37.4, 33.4,

26.5 (d, J = 33.0 Hz), 21.2 ppm. 11B{1H} NMR (128 MHz, CDCl3): δB 34.2 ppm.

2-(2-cyclopentylethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2i).

B O

O


δH 1.74 - 1.65 (m, 3H, CH2), 1.58 - 1.51 (m, 2H, CH2), 1.49 - 1.44 (m, 1H, CH), 1.39 (q, J = 8.0

Hz, 2H, CH2), 1.23 (s, 12H, CH3), 1.10 - 1.03 (m, 2H, CH2), 0.76 (t, J = 8.0 Hz, 2H, CH2) ppm. 13C{1H} NMR (100 MHz, CDCl3): δC 82.8, 42.6, 32.3, 30.1, 25.2, 24.7 ppm. 11B{1H} NMR (128

MHz, CDCl3): δB 33.1 ppm

4,4,5,5-tetramethyl-2-octyl-1,3,2-dioxaborolane (2j).

B O

O


δH 1.39 - 1.34 (m, 2H, CH2), 1.27 - 1.24 (m, 10H, CH2), 1.22 (s, 12H, CH3), 0.85 (t, J = 8.0 Hz,

2H, CH3), 0.74 (t, J = 8.0 Hz, 2H, CH2) ppm. 13C{1H} NMR (100 MHz, CDCl3): δC 82.7, 32.4,

31.8, 29.3 (d, J = 13.0 Hz), 24.7, 23.9, 22.6, 14.0 ppm. 11B{1H} NMR (128 MHz, CDCl3):

δB34.1 ppm.

2-(5-bromopentyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2k).

B O

OBr


δH 3.40 (t, J = 8.0 Hz, 2H, CH2), 1.85 (t, J = 8.0 Hz, 2H, CH2), 1.45 - 1.41 (q, 4H, CH2), 1.24 (s,

12H, CH3), 0.78 (t, J = 8.0 Hz, 2H, CH2) ppm. 13C{1H} NMR (100 MHz, CDCl3): δC 83.0 (d, J =

15.0 Hz), 33.9, 32.6, 30.8, 24.7, 23.1 ppm. 11B{1H} NMR (128 MHz, CDCl3): δB 33.3 ppm.

2-(6-bromohexyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2l)

BO

OBr


δH 3.38 (t, J = 8.0 Hz, 2H, CH2), 1.87 - 1.80 (q, 2H, CH2), 1.45 - 1.37 (m, 4H, CH2), 1.33 - 1.28

(m, 2H, CH2), 1.23 (s, 12H, CH3), 0.76 (t, J = 8.0 Hz, 2H, CH2) ppm. 13C{1H} NMR (100 MHz,

CDCl3): δC 82.8, 33.9, 32.6, 31.3, 27.8, 24.7, 23.7 ppm. 11B{1H} NMR (128 MHz, CDCl3): δB

34.4 ppm.

2-(8-bromooctyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2m).

B O

O

Br

Yield: [Mass in 319.09 mg (100%), Mass out 280.79 mg (88%)]. 1H NMR (400 MHz, CDCl3) H

3.37 (t, 2H), 1.84 - 1.80 (m, 2H), 1.39 - 1.36 (m, 4H), 1.29 – 1.27 (m, 6H), 1.22 (s, 12H), 0.74 (t,

2H) ppm. 13C(1H) NMR (100 MHz, CDCl3) C 82.7, 33.9, 32.7, 32.1, 29.0, 28.5, 28.0, 24.7, 23.8

ppm. 11B(1H) NMR (128 MHz, CDCl3) B 34.0 ppm.

2-(2,3-dimethylbutyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2n).

B O

O


71.58 - 1.53 (m, 1H), 1.47 – 1.42 (m, 1H), 1.22 (s, 12H), 0.83 - 0.78 (m, 10H), 0.61 – 0.55 (m,

1H) ppm. 13C(1H) NMR (100 MHz, CDCl3) C 82.7, 35.0, 34.1, 24.8, 24.6, 19.7, 18.6 ppm.

11B(1H) NMR (128 MHz, CDCl3) B 34.3ppm.

4-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethyl)phenyl acetate (2o). 3

B O

O

O

O


7.21 (d, 2H), 6.96 (d, 2H), 2.74 (t, 2H), 2.27 (s, 3H), 1.21 (s, 12H), 1.13 (t, 2H) ppm. 13C(1H)

NMR (100 MHz, CDCl3) C 169.6, 148.4, 141.8, 128.8, 121.0, 83.0, 29.2, 24.7, 21.0 ppm.

11B(1H) NMR (128 MHz, CDCl3) B 34.2 ppm.

(E)-4,4,5,5-tetramethyl-2-styryl-1,3,2-dioxaborolane (3a). 4

B O

O

Yield: [Mass in 230.11 mg (100%), Mass out 227.8 mg (99%)]. 1H NMR (400 MHz, CDCl3): H 7.42 -

7.40 (m, 2H), 7.36, (d, 1H, J = 16 Hz), 7.25 - 7.20 (m, 3H), 6.10 (d, 1H, J = 16 Hz), 1.24 (s, 12H, CH3,

Bpin) ppm. 13C{1H} NMR (100 MHz, CDCl3): C 148.0, 133.5, 131.7, 131.6, 128.5, 122.9, 83.4, 24.5

ppm. 11B{1H} NMR (128.3 MHz, CDCl3): B 30.4 (C-Bpin) ppm.

(E)-4,4,5,5-tetramethyl-2-(4-methylstyryl)-1,3,2-dioxaborolane (3b). 4

B O

O

Yield: [Mass in 244.14 mg (100%), Mass out 239.3 mg (98%)]. 1H NMR (400 MHz, CDCl3) H 7.42 -

7.37 (m, 3H), 7.15 (d, J = 8 Hz, 2H), 6.13 (d, J = 20.0 Hz, 1H), 2.35 (s, 3H), 1.32 (s, 12H) ppm. 13C{1H}

NMR (100 MHz, CDCl3) C 149.5, 138.9, 134.8, 132.0, 129.3,127.0, 83.2, 24.8, 21.3 ppm. 11B{1H}

NMR (128.3 MHz, CDCl3) B 29.9 ppm.

(E)-2-(4-methoxystyryl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3c). 4

B O

O

MeO

Yield: [Mass in 260.2 mg (100%), Mass out 206 mg (82%)]. 1H NMR (400 MHz, CDCl3) H 7.36 (d, J =

8 Hz, 2H), 7.33 (d, J = 20 Hz, 1H), 6.77 (d, J = 8 Hz, 2H), 5.95 (d, J = 20 Hz, 1H), 3.68 (s, 3H), 1.22 (s,

12H) ppm. 13C{1H} NMR (100 MHz, CDCl3) C 160.3, 149.1, 133.5, 129.0, 128.4, 114.0, 83.2, 55.2, 24.8

ppm. 11B{1H} NMR (128.3 MHz, CDCl3): B 29.9(C-Bpin) ppm.

(E)-2-(4-chlorostyryl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3e). 4

B O

O

Cl

Yield: [Mass in 309.1 mg (100%), Mass out 302.9 mg (98%)]. 1H NMR (400 MHz, CDCl3): H

7.48 - 7.44 (m, 2H, ArH), 7.36 (d, 1H, J = 20 Hz), 7.04 - 7.00 (m, 2H, ArH), 6.07 (d, 1H, J =20

Hz), 1.31 (s, 12H, CH3, Bpin) ppm. 13C{1H} NMR (100 MHz, CDCl3): C 164.3, 161.9, 148.1,

133.7, 128.7, 115.6, 83.4, 24.8 ppm. 11B{1H} NMR (128.3 MHz, CDCl3): B 29.7 (C-Bpin) ppm.

(E)-2-(4-bromostyryl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3e). 4

B O

O

Br


7.46 - 7.44 (m, 2H, ArH), 7.35 - 7.30 (m, 3H, ArH), 6.15 (d, 1H, J = 20 Hz), 1.31 (s, 12H, CH3,

Bpin) ppm. 13C{1H} NMR (100 MHz, CDCl3): C 160.3, 149.1, 133.5, 129.0, 128.4, 113.9, 83.2,

24.8 ppm. 11B{1H} NMR (128.3 MHz, CDCl3): B 29.8 (C-Bpin) ppm.

(E)-2-(2-cyclohexylvinyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3f). 4

B O

O

Yield: [Mass in 236.2 mg (100%), Mass out 229.11 mg (97%)]. 1H NMR (400 MHz, CDCl3): H 6.59 (dd,

1H, JHH =12 Hz, 8 Hz), 5.38 (d, 1H, J =20 Hz), 2.03 - 2.01 (m, 1H), 1.75 - 1.71 (m, 6H), 1.27 (s, 12H,

CH3, Bpin) 1.25 - 1.03 (m, 4H), ppm. 13C{1H} NMR (100 MHz, CDCl3): C 159.8, 82.9, 43.2, 31.9, 26.1,

25.9, 24.7, 24.5 ppm. 11B{1H} NMR (128.3 MHz, CDCl3): B 30.4 (C-Bpin) ppm.

(E)-2-(2-cyclopentylvinyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3g). 4

B O

O


H 6.63 (dd, 1H, JHH =12 Hz, 8 Hz), 5.42 (d, 1H, J = 20 Hz), 2.56 - 2.54 (m, 1H), 1.81 - 1.65(m,

6H), 1.59 - 1.39 (m, 2H), 1.23 (s, 12H, CH3, Bpin) ppm. 13C{1H} NMR (100 MHz, CDCl3): C

158.9, 82.9, 46.1, 32.3, 25.4, 24.7, 24.5 ppm. 11B{1H} NMR (128.3 MHz, CDCl3): B 30.6 (C-

Bpin) ppm.

(E)-4,4,5,5-tetramethyl-2-(2-(thiophen-3-yl)vinyl)-1,3,2-dioxaborolane (3h). 4

B O

O

S


H 7.305 (d, J =20, 1H), 7.28 – 7.27 (m, 2H, ArH), 7.24 – 7.24 (m, 1H, ArH), 5.93 (d, J = 20 Hz,

1H), 1.28 (s, 12H, CH3, Bpin) ppm. 13C-{1H} NMR (100 MHz, CDCl3): C 143.0, 141.1, 126.0,

124.9 83.2, 24.7ppm. 11B{1H} NMR (128.3 MHz, CDCl3): B 29.6 (C-Bpin) ppm.

(E)-2-(5-chloropent-1-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2j).

Cl Bpin

The compound was isolated as a colourless oil. Yield: [Mass in 230.12 mg (100%), Mass out 227.82 mg

(99%)]. 1H NMR (400 MHz, CDCl3): H 6.61 - 6.53 (m, 1H), 5.48 (d, 1H, J = 20 Hz), 3.52 (t, 2H, J = 8

Hz), 2.34 - 2.27 (m, 2H), 1.92 - 1.85 (m, 2H), 1.25 (s, 12H, CH3, Bpin) ppm. 13C{1H} NMR (100 MHz,

CDCl3): C 152.0, 83.0, 44.2, 32.6, 30.9, 24.5 ppm. 11B{1H} NMR (128.3 MHz, CDCl3): B 31.6 (C-Bpin)

ppm.

(E)-trimethyl(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)vinyl)silane (3j). 4

SiB O

O


6.02 (d, J.=8 Hz, 1H), 5.84 (d, 4Hz, 1H), 1.27 (s, 12H, CH3, Bpin), 0.07 (s, 9H, SiMe3) ppm. 13C{1H} NMR (100 MHz, CDCl3): C 157.8, 134.4, 83.0, 24.5, -1.88 ppm. 11B{1H} NMR (128.3

MHz, CDCl3): B 30.9 (C-Bpin) ppm.

(E)-4-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)vinyl)phenyl acetate (3k). 1

B O

O

O

O

Yield: [Mass in 288.15 mg (100%), Mass out 273.75 mg (95%)]. 1H NMR (400 MHz, CDCl3): H 7.88 -

7.86 (m, 2H), 7.41 - 7.39 (m, 2H), 7.07 (d, J = 20 Hz, 1H), 6.15 (d, J = 16Hz, 1H) 3.77 (s, 3H, OCH3),

1.18 (s, 12H, CH3, Bpin) ppm. 13C{1H} NMR (100 MHz, CDCl3): C 166.7, 148.1, 141.7, 129.9, 129.0,

126.8, 125.2, 83.5, 52.0, 24.8 ppm. 11B{1H} NMR (128.3 MHz, CDCl3): B 29.5 (C-Bpin) ppm.

9 8 7 6 5 4 3 2 1Chemical Shift (ppm)

2.48

11.9

9

2.01

0.99

4.05

7.26

7.24

7.23

7.21

7.20

7.16

7.15

7.14

2.76

2.74

2.72

1.21

1.16

1.14

1.12

Figure FS4. 1H NMR (400 MHz, CDCl3) spectrum of 2a.

B O

O

96 88 80 72 64 56 48 40 32 24 16 8 0 -8 -16 -24 -32 -40 -48 -56 -64 -72 -80 -88 -96 -104ppm

33.8

6

Figure FS5. 11B{1H} NMR (128 MHz, CDCl3) spectrum of 2a

190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20Chemical Shift (ppm)

144.

33

128.

1012

7.93

125.

42

83.0

077

.31

77.0

076

.68

29.8

8

24.7

4

Figure FS6. 13C{1H} NMR (100 MHz, CDCl3) spectrum of 2a.

B O

O

B O

O


2.06

12.2

9

3.00

2.07

1.95

1.91

7.27

7.16

7.14

7.12

7.10

2.78

2.76

2.74

2.35

1.27

1.19

1.17

1.15

Figure FS7. 1H NMR (400 MHz, CDCl3) spectrum of 2b.

96 88 80 72 64 56 48 40 32 24 16 8 0 -8 -16 -24 -32 -40 -48 -56 -64 -72 -80 -88 -96 -104ppm

34.0

0

Figure FS8. 11B{1H} NMR (128 MHz, CDCl3) spectrum of 2b.

B O

O

B O

O


141.

30

134.

7312

8.78

127.

77

82.9

777

.32

77.0

076

.69

29.4

424

.73

20.8

9

Figure FS9. 13C{1H} NMR (100 MHz, CDCl3) spectrum of 2b.

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0Chemical Shift (ppm)

2.18

12.2

3

2.03

2.98

1.95

1.93

7.27

7.16

7.14

6.83

6.81

3.78

2.73

2.71

2.69

1.23

1.15

1.13

1.11

Figure FS10. 1H NMR (400 MHz, CDCl3) spectrum of 2c.

B O

O

B O

O

MeO

96 88 80 72 64 56 48 40 32 24 16 8 0 -8 -16 -24 -32 -40 -48 -56 -64 -72 -80 -88 -96 -104ppm

33.9

2

Figure FS11. 11B{1H} NMR (128 MHz, CDCl3) spectrum of 2c.


157.

47

136.

45

128.

76

113.

50

82.9

577

.31

77.0

076

.68

55.1

0

28.9

624

.71

Figure FS12. 13C{1H} NMR (100 MHz, CDCl3) spectrum of 2c.

B O

O

MeO

B O

O

MeO

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0Chemical Shift (ppm)

2.28

12.1

58.

99

2.00

1.88

1.88

7.33

7.31

7.27

7.20

7.18

2.78

2.76

2.74

1.34

1.26

1.20

1.18

1.16

Figure FS13. 1H NMR (400 MHz, CDCl3) spectrum of 2d.

100 90 80 70 60 50 40 30 20 10 0 -10 -20 -30 -40 -50 -60 -70 -80 -90 -100ppm

34.1

7

Figure FS14. 11B{1H} NMR (128 MHz, CDCl3) spectrum of 2d.

B O

O

B O

O


148.

15

141.

27

127.

5812

4.98

82.9

877

.32

77.0

076

.68

34.2

431

.38

29.3

224

.75

Figure FS15. 13C{1H} NMR (100 MHz, CDCl3) spectrum of 2d.

10 9 8 7 6 5 4 3 2 1Chemical Shift (ppm)

12.152.112.04

7.27

7.18

7.17

7.16

7.15

6.96

6.94

6.92

2.74

2.72

2.70

1.21

1.14

1.12

1.10

Figure FS16. 1H NMR (400 MHz, CDCl3) spectrum of 2e.

B O

O

B O

O

F

100 90 80 70 60 50 40 30 20 10 0 -10 -20 -30 -40 -50 -60 -70 -80 -90 -100ppm

33.5

1

Figure FS17. 11B{1H} NMR (128 MHz, CDCl3) spectrum of 2e.


162.

2615

9.84

139.

9213

9.88

129.

3012

9.23

114.

8611

4.66

83.0

977

.31

77.0

076

.68

29.1

124

.74

Figure FS18. 13C{1H} NMR (100 MHz, CDCl3) spectrum of 2e.

B O

O

F

B O

O

F


12.122.242.14

7.38

7.36

7.27

7.10

7.08

2.72

2.70

2.68

1.22

1.13

1.11

1.09

Figure FS19. 1H NMR (400 MHz, CDCl3) spectrum of 2f.

100 90 80 70 60 50 40 30 20 10 0 -10 -20 -30 -40 -50 -60 -70 -80 -90 -100ppm

34.0

0

Figure FS20. 11B{1H} NMR (128 MHz, CDCl3) spectrum of 2f.

B O

O

Br

B O

O

Br


143.

27

131.

1112

9.76

119.

11

83.1

277

.31

77.0

076

.68

29.3

224

.74

Figure FS21. 13C{1H} NMR (100 MHz, CDCl3) spectrum of 2f.


2.08

12.1

9

2.02

7.27

2.80

2.78

2.75

1.22

1.11

1.09

1.06

Figure FS22. 1H NMR (400 MHz, CDCl3) spectrum of 2g.

B O

O

Br

B O

O

F

FF

FF

96 88 80 72 64 56 48 40 32 24 16 8 0 -8 -16 -24 -32 -40 -48 -56 -64 -72 -80 -88 -96 -104ppm

33.2

2

Figure FS23. 11B{1H} NMR (128 MHz, CDCl3) spectrum of 2g.

-20 -40 -60 -80 -100 -120 -140 -160 -180 -200

-144

.47

-144

.51

-159

.04

-159

.10

-163

.57

-163

.61

Figure FS24. 19F{1H} NMR (376 MHz, CDCl3) spectrum of 2g.

B O

O

F

FF

FF

B O

O

F

FF

FF

200 180 160 140 120 100 80 60 40 20 0

146.

2314

6.13

146.

0314

3.70

143.

6014

0.55

138.

5713

8.05

136.

0913

6.02

117.

3311

7.18

116.

99

83.3

677

.30

76.9

876

.66

24.6

9

16.9

1

Figure FS25. 13C{1H} NMR (100 MHz, CDCl3) spectrum of 2g.

11 10 9 8 7 6 5 4 3 2 1 0

2.132.215.4613.382.025.89

7.27

1.69

1.66

1.25

1.22

1.22

1.17

1.16

1.15

1.14

0.74

0.72

0.70

Figure FS26. 1H NMR (400 MHz, CDCl3) spectrum of 2h.

B O

O

F

FF

FF

B O

O

80 72 64 56 48 40 32 24 16 8 0 -8 -16 -24 -32 -40

34.1

7

Figure FS27. 11B{1H} NMR (128 MHz, CDCl3) spectrum of 2h.

180 160 140 120 100 80 60 40 20 0

82.7

977

.35

77.0

376

.71

40.4

137

.46

33.3

926

.75

26.4

224

.78

21.2

8

Figure FS28. 13C{1H} NMR (100 MHz, CDCl3) spectrum of 2h.

B O

O

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5Chemical Shift (ppm)

1.68

1.88

4.18

12.0

51.

634.

18

7.27

1.68

1.66

1.63

1.62

1.39

1.22

1.17

1.16

1.15

1.15

1.14

0.74

0.72

0.70

Figure FS29. 1H NMR (400 MHz, CDCl3) spectrum of 2i.

75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0 -5 -10

33.2

1

Figure FS30. 11B{1H} NMR (128 MHz, CDCl3) spectrum of 2i.

B O

O

B O

O


82.7

677

.32

77.0

076

.69

40.3

837

.44

33.3

626

.72

26.3

924

.75

24.5

021

.25

Figure FS31. 13C{1H} NMR (100 MHz, CDCl3) spectrum of 2i.


1.88

2.06

11.9

02.

031.

352.

152.

85

7.27

2.16

1.71

1.70

1.69

1.68

1.56

1.47

1.40

1.38

1.23

1.05

0.78

0.76

0.74

Figure FS32. 1H NMR (400 MHz, CDCl3) spectrum of 2j.

B O

O

B O

O

75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0 -5 -10 -15

33.1

6

Figure FS33. 11B{1H} NMR (128 MHz, CDCl3) spectrum of 2j.


82.7

977

.32

77.0

076

.68

42.5

9

32.2

930

.11

25.1

724

.76

Figure FS34. 13C{1H} NMR (100 MHz, CDCl3) spectrum of 2j.

B O

O

B O

O


2.14

3.40

12.0

010

.38

2.36

7.27

1.38

1.36

1.27

1.24

1.22

0.87

0.85

0.83

0.76

0.74

0.72

Figure FS35. 1H NMR (400 MHz, CDCl3) spectrum of 2k.

96 88 80 72 64 56 48 40 32 24 16 8 0 -8 -16 -24 -32 -40 -48 -56 -64 -72 -80 -88 -96 -104ppm

34.1

7

Figure FS36. 11B{1H} NMR (128 MHz, CDCl3) spectrum of 2k.

BO

O

BO

O


82.7

477

.31

77.0

076

.68

32.3

831

.85

29.3

429

.21

24.7

523

.95

22.6

314

.05

Figure FS37. 13C{1H} NMR (100 MHz, CDCl3) spectrum of 2k.


2.09

12.4

94.

19

1.92

2.00

7.27

3.41

3.40

3.38

1.87

1.85

1.83

1.45

1.44

1.43

1.42

1.41

1.24

0.80

0.78

0.77

Figure FS38. 1H NMR (400 MHz, CDCl3) spectrum of 2l.

BO

O

BO

OBr

75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0 -5 -10 -15

33.3

7

Figure FS39. 11B{1H} NMR (128 MHz, CDCl3) spectrum of 2l.


83.1

082

.95

77.3

177

.00

76.6

8

33.9

632

.60

30.7

724

.77

23.1

4

Figure FS40. 13C{1H} NMR (100 MHz, CDCl3) spectrum of 2l.

BO

OBr

BO

OBr


2.00

12.1

32.

294.

12

2.22

2.07

7.27

3.40

3.38

3.36

1.85

1.83

1.81

1.43

1.42

1.40

1.38

1.37

1.31

1.30

1.23

0.78

0.76

0.74

Figure FS41. 1H NMR (400 MHz, CDCl3) spectrum of 2m.

75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0 -5 -10 -15

34.4

5

Figure FS42. 11B{1H} NMR (128 MHz, CDCl3) spectrum of 2m.

BBr

O

O

BBr

O

O


82.8

577

.32

77.0

076

.69

33.9

332

.65

31.3

327

.86

24.7

523

.69

Figure FS43. 13C{1H} NMR (100 MHz, CDCl3) spectrum of 2m.


2.00

12.0

15.

954.

83

2.12

1.98

7.27

3.39

3.37

3.36

1.84

1.82

1.80

1.39

1.38

1.37

1.36

1.29

1.27

1.22

0.76

0.74

0.72

Figure FS44. 1H NMR (400 MHz, CDCl3) spectrum of 2n.

BBr

O

O

BO

OBr

75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0 -5 -10 -15

34.0

8

Figure FS45. 11B{1H} NMR (128 MHz, CDCl3) spectrum of 2n.


82.7

777

.32

77.0

076

.68

33.9

432

.77

32.1

829

.09

28.5

928

.09

24.7

423

.85

Figure FS46. 13C{1H} NMR (100 MHz, CDCl3) spectrum of 2n.

BO

OBr

BO

OBr


1.06

10.4

2

12.0

31.

061.

04

7.27

1.58

1.48

1.47

1.45

1.23

1.23

0.84

0.83

0.83

0.81

0.81

0.79

Figure FS47. 1H NMR (400 MHz, CDCl3) spectrum of 2o.

96 88 80 72 64 56 48 40 32 24 16 8 0 -8 -16 -24 -32 -40 -48 -56 -64 -72 -80 -88 -96 -104ppm

34.3

2

Figure FS48. 11B{1H} NMR (128 MHz, CDCl3) spectrum of 2o.

B O

O

B O

O


82.7

577

.31

77.0

076

.68

35.0

534

.16

24.8

524

.66

19.7

118

.60

Figure FS49. 13C{1H} NMR (100 MHz, CDCl3) spectrum of 2o.


2.02

12.3

0

3.09

1.96

1.86

2.00

7.27

7.22

7.20

6.97

6.95

2.76

2.74

2.71

2.27

1.21

1.15

1.13

1.11

Figure FS50. 1H NMR (400 MHz, CDCl3) spectrum of 2p.

B O

O

B O

O

O

O

75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0 -5 -10 -15

34.2

5

Figure FS51. 11B{1H} NMR (128 MHz, CDCl3) spectrum of 2p.


169.

63

148.

43

141.

85

128.

82

121.

04

83.0

777

.32

77.0

076

.68

29.2

424

.70

21.0

2

Figure FS52. 13C{1H} NMR (100 MHz, CDCl3) spectrum of 2p.

B O

O

O

O

B O

O

O

O


70 65 60 55 50 45 40 35 30 25 20 15 10 5 0 -5 -10 -15

30.4

0

Figure FS54. 11B{1H} NMR (128 MHz, CDCl3) spectrum of 3a.

B O

O

B O

O

180 160 140 120 100 80 60 40 20 0

148.

0213

6.36

133.

5113

1.71

131.

5612

8.99

128.

4712

8.18

122.

86

83.4

377

.32

77.0

076

.69

24.5

2


12 11 10 9 8 7 6 5 4 3 2 1 0

12.333.031.062.083.27

7.42

7.41

7.41

7.39

7.38

7.37

7.16

7.14

6.15

6.11

2.35

1.32


B O

O

B O

O

70 65 60 55 50 45 40 35 30 25 20 15 10 5 0 -5 -10 -15

29.9

1

Figure FS57. 11B{1H} NMR (128 MHz, CDCl3) spectrum of 3b.

Figure FS58. 13C{1H} NMR (100 MHz, CDCl3) spectrum of 3b.

B O

O

B O

O

Figure FS59. 1H NMR (400 MHz, CDCl3) spectrum of 3c.

Fig70 65 60 55 50 45 40 35 30 25 20 15 10 5 0 -5 -10 -15

29.9

1

ure FS60. 11B{1H} NMR (128 MHz, CDCl3) spectrum of 3c.

B O

O

MeO

B O

O

MeO

Figure FS61. 13C{1H} NMR (100 MHz, CDCl3) spectrum of 3c.

11 10 9 8 7 6 5 4 3 2 1 0

11.450.982.061.152.01

7.48

7.46

7.46

7.44

7.38

7.33

7.26

7.04

7.02

7.00

6.10

6.05

1.31

0.00

Figure FS62. 1H NMR (400 MHz, CDCl3) spectrum of 3d.

B O

O

MeO

B O

O

Cl

60 55 50 45 40 35 30 25 20 15

29.7

0Figure FS63. 11B{1H} NMR (128 MHz, CDCl3) spectrum of 3d.

200 180 160 140 120 100 80 60 40 20 0

164.

3816

1.91

148.

18

133.

7012

9.04

128.

7612

8.23

115.

6711

5.45

83.4

177

.37

77.0

676

.74

24.8

0

Figure FS64. 13C{1H} NMR (100 MHz, CDCl3) spectrum of 3d.

B O

O

Cl

B O

O

Cl

11 10 9 8 7 6 5 4 3 2 1 0

11.790.992.962.06

7.43

7.41

7.31

7.31

7.29

7.26

6.14

6.09

1.27

Figure FS65. 1H NMR (400 MHz, CDCl3) spectrum of 3e.

60 55 50 45 40 35 30 25 20 15

29.8

0

Figure FS66. 11B{1H} NMR (128 MHz, CDCl3) spectrum of 3e.

B O

O

Br

B O

O

Br

180 160 140 120 100 80 60 40 20 0

146.

96

135.

3613

0.71

127.

47

121.

84

82.4

176

.34

76.0

375

.71

23.7

8

Figure FS67. 13C{1H} NMR (100 MHz, CDCl3) spectrum of 3e.

B O

O

Br

12 11 10 9 8 7 6 5 4 3 2 1 0

3.9513.466.371.061.001.01

7.27

6.61

6.60

6.57

6.55

5.40

5.40

5.36

2.03

1.75

1.74

1.73

1.73

1.72

1.71

1.27

1.25

1.25

1.11

0.07

Figure FS68. 1H NMR (400 MHz, CDCl3) spectrum of 3f.

60 55 50 45 40 35 30 25 20 15 10 5 0

30.4

0

Figure FS69. 11B{1H} NMR (128 MHz, CDCl3) spectrum of 3f.

B O

O

B O

O

180 160 140 120 100 80 60 40 20 0

159.

86

82.9

877

.34

77.0

376

.71

43.2

5

31.9

226

.17

25.9

624

.78

24.5

6

Figure FS70. 13C{1H} NMR (100 MHz, CDCl3) spectrum of 3f.

11 10 9 8 7 6 5 4 3 2 1 0

12.212.135.971.020.870.89

7.29

6.66

6.64

6.61

6.60

5.44

5.40

2.56

2.54

1.81

1.79

1.66

1.65

1.59

1.58

1.57

1.39

1.28

1.23

0.02

Figure FS71. 1H NMR (400 MHz, CDCl3) spectrum of 3g.

B O

O

B O

O

80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0 -5

30.6

0

Figure FS72. 11B{1H} NMR (128 MHz, CDCl3) spectrum of 3g.

200 180 160 140 120 100 80 60 40 20 0

158.

92

82.9

777

.35

77.0

376

.71

46.1

8

32.3

425

.24

24.7

624

.53

Figure FS73. 13C{1H} NMR (100 MHz, CDCl3) spectrum of 3g.

B O

O

B O

O

Figure FS74. 1H NMR (400 MHz, CDCl3) spectrum of 3h.

85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0

29.6

0

Figure FS75. 11B{1H} NMR (128 MHz, CDCl3) spectrum of 3h.

B O

O

S

B O

O

S

Figure FS76. 13C{1H} NMR (100 MHz, CDCl3) spectrum of 3h.

Cl BO

O

B O

O

S

Figure FS77. 1H NMR (400 MHz, CDCl3) spectrum of 3i.

85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 531

.60

Figure FS78. 11B{1H} NMR (128 MHz, CDCl3) spectrum of 3i.

Cl BO

O

Cl BO

O

Figure FS79. 13C{1H} NMR (100 MHz, CDCl3) spectrum of 3i.

12 11 10 9 8 7 6 5 4 3 2 1 0

8.9412.280.970.99

7.26

6.03

6.01

5.85

5.84

1.27

0.07

Figure FS80. 1H NMR (400 MHz, CDCl3) spectrum of 3j.

SiB O

O

55 50 45 40 35 30 25 20 15 10 5

30.9

0

Figure FS81. 11B{1H} NMR (128 MHz, CDCl3) spectrum of 3j.

180 160 140 120 100 80 60 40 20 0

157.

86

134.

48

83.0

877

.31

77.0

076

.68

24.7

924

.53

0.24

-1.8

8

Figure FS82. 13C{1H} NMR (100 MHz, CDCl3) spectrum of 3j.

SiB O

O

SiB O

O

Figure FS83. 1H NMR (400 MHz, CDCl3) spectrum of 3k.

80 72 64 56 48 40 32 24 16 8 0 -8 -16

29.5

0

Figure FS84. 11B{1H} NMR (128 MHz, CDCl3) spectrum of 3k.

B O

O

O

O

B O

O

O

O

200 180 160 140 120 100 80 60 40 20 0

166.

75

148.

13

141.

72

129.

9112

9.02

126.

8912

5.29

83.5

577

.40

77.0

876

.76

52.0

8

24.8

0

Figure FS85. 13C{1H} NMR (100 MHz, CDCl3) spectrum of 3k.

11 10 9 8 7 6 5 4 3 2 1 0

10.993.301.830.931.94

7.30

7.28

7.15

7.13

7.07

7.06

7.04

7.02

2.25

1.21

0.00


B O

O

O

O

H B

D

OO

200 180 160 140 120 100 80 60 40 20 0

148.

26

136.

6613

2.01

128.

77

123.

14

83.7

177

.63

77.3

277

.00

24.8

2


11 10 9 8 7 6 5 4 3 2 1 0

12.153.101.99

7.38

7.37

7.36

7.36

7.26

7.25

7.24

7.23

2.26

1.22

0.00

-0.0

8


H B

D

Br

OO

H B

D

OO

Figur200 180 160 140 120 100 80 60 40 20 0

147.

94

136.

3413

1.68

128.

45

122.

82

83.3

977

.31

77.0

076

.68

24.7

6

e FS89. 13C{1H} NMR (100 MHz, CDCl3) spectrum of 4b.

Figure FS90. 31P{1H} NMR spectrum (161.9 MHz, 25°C, C6D6) reaction mixture

H B

D

Br

OO

Reference:

1. S. Kisan, V. Krishnakumar and C. Gunanathan, ACS Catal. 2017, 7, 5950-5954.2. A. Bismuto, M. J. Cowley and S. P. Thomas, ACS Catal. 2018, 8, 2001-2005.3. G. Zhang, H. Zeng, J. Wu, Z. Yin, S. Zheng, and J. C. Fettinger. Angew. Chem. Int. Ed.

2016, 55, 14369 –14372.4. S. Mandal, P. K. Verma and K. Geetharani, Chem. Commun., 2018, 54, 13690-13693.

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