Application of beta zeolite in allylation reaction aiming formation of new C-C bonds

Macedo, V. K. S. A.; Santos, C. S.; Mello, M. I. S. de; Alves, J. A. B. L. R.; Barros, J. M. F.; Freitas, J. C. R.

doi:10.1590/0366-69132020663792553

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Articles • Cerâmica 66 (379) • Jul-Sep 2020 • https://doi.org/10.1590/0366-69132020663792553 copy

Application of beta zeolite in allylation reaction aiming formation of new C-C bonds

Aplicação de zeólita beta na catálise da reação de alilação visando formação de novas ligações C-C

Authorship SCIMAGO INSTITUTIONS RANKINGS

Abstract

This study describes the formation of new C-C bonds through the allylation reaction of different aldehydes promoted by beta zeolite. This environmentally friendly method was characterized by its efficiency, versatility, and chemoselectivity in the formation of different homoallylic alcohols. Homoallylic alcohols were obtained in good yields (80% to 96%), short reaction times (30 to 75 min) at room temperature, and without the need for additional purifications. In addition, water was used as a co-solvent, ensuring the method a development in the field of green chemistry. Moreover, it was found that the zeolite beta can be reused for up to one reaction cycle without loss of its efficiency.

Keywords:
chemical catalysis; allylation reaction; homoallylic alcohols; beta zeolite

Table I Effect of H2O:CH2Cl2 ratio on the allylation of p-nitrobenzaldehyde (1a) by potassium allyltrifluoroborate (2) at room temperature.


Experiment^a	Ratio H₂O:CH₂Cl₂	Time (min)	Yield^b (%)
1	2.5 mL:0 mL	30	81
2	2.25 mL:0.25 mL	30	84
3	1.25 mL:1.25 mL	30	90
4	0.25 mL:2.25 mL	30	95
5	0 mL:2.5 mL	30	69^c

Table II Effect of beta zeolite amount on the allylation of p-nitrobenzaldehyde (1a) by potassium allyltrifluoroborate (2) in 10:90 H2O:CH2Cl2 at room temperature.


Experiment^a	Beta zeolite (% m/m)	Time (min)	Yield^b (%)
1	150	30	80^c
2	100	30	95
3	75	30	94
4	50	40	91
5	25	60	60^c
6	-^c	60	29^c

Table V Beta zeolite (100% m/m) recycling after successive reactions of allylation.


Experiment	Cycle	Time (min)	Yield (%)
1	-	30	95
2	1	40	91
3	2	90	51ª
4	3	90	45^a

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Experiment	Aldehyde		Product		Time (min)	Yield^a (%)
1		1a		3a	30	95
2		1b		3b	30	91
3		1c		3c	30	94
4		1d		3d	45	89
5		1e		3e	50	92
6		1f		3f	75	96
7		1g		3g	40	91
8		1h		3h	40	92
9		1i		3i	40	89
10		1j		3j	60	91
11		1k		3k	75	92
12		1l		3l	60	80

Homoallylic alcohol		1H NMRa (300 MHz, CDCl3)	13C NMRa (75 MHz, CDCl3)
	3a	δ 8.21 (d, J=8.4 Hz, 2H, H_Ar), 7.54 (d, J=8.4 Hz, 2H, H_Ar), 5.86-5.72 (m, 1H, CH=CH₂), 5.22-5.16 (m, 2H, CH=CH ₂), 4.86 (dd, J= 8.1, 4.5 Hz, 1H, CHOH), 2.61-2.40 (m, 2H, CHCH ₂), 2.08 (sl, 1H, OH)	δ 151.5, 147.5, 133.6, 126.9, 124.0, 119.9, 72.5, 44.2
	3b	δ 8.24 (s, 1H, H_Ar), 8.13 (d, J=8.1 Hz, 1H, H_Ar), 7.71 (d, J=7.8 Hz, 1H, H_Ar), 7.53 (dd, J= 8.1, 7.8 Hz, 1H, H_Ar), 5.88-5.73 (m, 1H, CH=CH₂), 5.22-5.16 (m, 2H, CH=CH ₂), 4.86 (dd, J= 7.8, 4.8 Hz, 1H, CHOH), 2.63-2.43 (m, 2H, CHCH ₂), 2.19 (s, l, 1H, OH)	δ 147.8, 145.5, 132.8, 131.5, 128.8, 122.0, 120.4, 119.1, 71.6, 43.4
	3c	δ 7.93 (d, J=8.1, 1H, H_Ar), 7.83 (dd, J=8.1 Hz, 1H, H_Ar), 7.65 (t, J=8.1 Hz, 1H, H_Ar), 7.43 (td, J= 8.1, 1.5 Hz, 1H, H_Ar), 5.97-5.83 (m, 1H, CH=CH₂), 5.31 (dd, J= 8.4, 3.6 Hz, 1H, CHOH), 5.24-5.18 (m, 2H, CH=CH ₂), 2.76-2.68 (m, 1H, CHCH ₂), 2.48-2.38 (m, 2H, CHCH ₂, OH)	δ 147.6, 139.2, 133.9, 133.4, 128.1, 128.0, 124.3, 119.0, 68.3, 42.8
	3d	δ 7.37-7.33 (m, 2H, H_Ar), 7.08-7.03 (m, 2H, H_Ar), 5.88-5.74 (m, 1H, CH=CH₂), 5.21-5.19 (m, 2H, CH=CH ₂), 4.75 (dd, 1H, J= 7.2, 5.7 Hz, CHOH), 2.53-2.38 (m, 2H, CHCH ₂), 1.90 (sl, 1H, OH)	δ 134.4, 127.8, 127.7, 119.0, 115.6, 115.4, 72.9, 44.3
	3e	δ 7.36-7.28 (m, 4H, H_Ar), 5.87-5.73 (m, 1H, CH=CH₂), 5.21-5.16 (m, 2H, CH=CH ₂), 4.74 (dd, J= 7.5, 5.4 Hz, CHOH), 2.57-2.42 (m, 2H, CHCH ₂), 2.12 (sl, 1H, OH)	δ 142.6, 134.3, 133.5, 128.9, 127.6, 119.2, 72.9, 44.2
	3f	δ 7,49 (d, J=8.4 Hz, 2H, H_Ar), 7.28-7.24 (m, 2H, H_Ar), 5.87-5.73 (m, 1H, CH=CH₂), 5.21-5.16 (m, 2H, CH=CH ₂), 4.73 (dd, J= 8.4, 4.4 Hz, 1H, CHOH), 2.58-2.41 (m, 2H, CH ₂CH=CH₂), 2.08 (sl, 1H, OH)	δ 143.2, 134.3, 131.9, 127.9, 121.6, 119.3, 73.0, 44.2
	3g	δ 7.28 (d, J=8.4 Hz, 2H, H_Ar), 6.88 (d, J=8.4 Hz, 2H, H_Ar), 5.86-5.72 (m, 1H, CH=CH₂), 5.18-5.11 (m, 2H, CH=CH ₂), 4.68 (t, J=6.6 Hz, CHOH), 3.80 (s, 3H, OMe), 2.51-2.47 (m, 2H, CHCH ₂), 2.00 (sl, 1H, OH)	δ 158.5, 135.6, 134.1, 126.6, 117.7, 113.3, 72.5, 54.8, 43.3
	3h	δ 7.8 (dd, J= 8.1, 7.8 Hz, 1H, H_Ar), 6.97-6.94 (m, 2H, H_Ar), 6.83 (ddd, J= 8.1, 2.7, 1.2 Hz, 1H, H_Ar), 5.85 (ddt, J= 17.1, 10.2, 7.5 Hz, 1H, CH=CH₂), 5.23-5.15 (m, 2H, CH=CH ₂), 4.74 (dd, J= 7.5, 5.4 Hz, 1H, CHOH), 3.84 (s, 3H, OMe), 2.56-2.50 (m, 2H, CHCH ₂), 2.06 (sl, 1H, OH)	δ 159.6, 145.6, 134.4, 129.3, 118.2, 118.0, 112.9, 111.2, 73.1, 55.1, 43.6
	3i	δ7.33 (dd, J= 7.5, 1.8 Hz, 1H, H_Ar), 7.28 (td, J= 7.5, 1.8 Hz, 1H, H_Ar), 6.95 (td, J= 8.4, 1.2 Hz, 1H, H_Ar), 6.87 (d, J=8.4 Hz, 1H, H_Ar), 5.85 (ddt, J= 17.1, 10.2, 7.5 Hz, 1H, CH=CH₂), 5.17-5.08 (m, 2H, CH=CH ₂), 4.95 (dd, J= 8.1, 5.1 Hz, 1H, CHOH), 3.84 (s, 3H, OMe), 2.64-2.44 (m, 2H, CHCH ₂), 2.41 (sl, 1H, OH)	δ 155.8, 134.7, 131.2, 127.7, 126.2, 120.1, 117.0, 109.9, 69.1, 54.7, 41.3
	3j	δ 7.63 (d, J=8.4 Hz, 2H, H_Ar), 7.47 (d, J=8.4 Hz, 2H, H_Ar), 5.82-5.72 (m, 1H, CH=CH₂), 5.19-5.14 (m, 2H, CH=CH ₂), 4.80 (dd, J= 8.4, 4.4 Hz, 1H, CHOH), 2.56-2.49 (m, 1H, CH ₂CH=CH₂), 2.47-2.41 (m, 1H, CH ₂CH=CH₂), 2.27 (sl, 1H, OH)	δ 149.1, 133.3, 132.2, 126.5, 119.5, 118.8, 111.1, 72.3, 43.8
	3k	δ 7.94 (d, J=8.0 Hz, 2H, H_Ar), 7.45 (d, J=8.0 Hz, 2H, H_Ar), 5.84-5.74 (m, 1H, CH=CH₂), 5.19-5.15 (m, 2H, CH=CH ₂), 4.81 (dd, J= 8.0, 5.2 Hz, 1H, CHOH), 2.59 (s, 3H, CH₃), 2.58-2.43 (m, 2H, CH ₂CH=CH₂), 2.21 (sl, 1H, OH)	δ 197.8, 149.1, 136.3, 133.7, 128.5, 125.9, 119.1, 72.6, 43.8, 26,6
	3l	δ 5.89-5.76 (m, 1H, CH=CH₂), 5.29-5.09 (m, 2H, CH=CH ₂), 3.68-3.59 (m, 1H, CHOH), 2.34-2.25 (m, 2H, CHCH ₂), 2.18-2.07 (m, 2H, CHOH) 1.66 (br s, 1H, OH), 1.50-1.25 (m, 6H, CH₃CH ₂CH ₂CH ₂), 0.87 (t, J=6.3 Hz, 6H, CH ₃CH₂)	δ 135.0, 118.1, 70.7, 42.0, 36.8, 31.9, 25.4, 22.7, 14.1