BNPs@Cur-Pd as a versatile and recyclable green nanocatalyst for Suzuki, Heck and Stille coupling reactions

Figures & data

Scheme 1. Stepwise preparation of BNPs@Cur-Pd nanocatalyst from BNPs and curcumin schematically.

Figure 1. FT-IR spectra of BNPs@Cur and BNPs@Cur-Pd nanocatalyst.

Figure 2. N₂ adsorption–desorption isotherms (a) and the corresponding pore size distributions (b) for BNPs@Cur-Pd nanocatalyst.

Figure 3. XRD patterns for BNPs@Cur and BNPs@Cur-Pd nanocatalyst.

Figure 4. SEM images of (a) BNPs@Cur and (b) BNPs@Cur-Pd nanocatalyst.

Figure 5. TEM images of BNPs@Cur-Pd nanocatalyst.

Figure 6. X-ray mapping analysis and EDX spectra for BNPs@Cur.

Figure 7. X-ray mapping analysis and EDX spectra for BNPs@Cur-Pd nanocatalyst.

Figure 8. TG-DTA thermogram of BNPs@Cur-Pd nanocatalyst.

Table 1. Optimization of the reaction conditions for Suzuki coupling reaction in the presence of BNPs@Cur-Pd as a nanocatalyst.^a

Entry	Catalyst (mg)	Solvent	Base	Temperature (^oC)	Time (min)	Yield (%)^b
1	–	PEG	Na2CO3	80	120	N.R.
2	5	PEG	Na2CO3	80	90	47
3	10	PEG	Na2CO3	80	90	91
4	12	PEG	Na2CO3	80	60	96
5	15	PEG	Na2CO3	80	55	97
6	12	H2O	Na2CO3	80	100	54
7	12	DMF	Na2CO3	80	70	93
8	12	DMSO	Na2CO3	80	50	92
9	12	PEG	KOH	80	100	81
10	12	PEG	Et3N	80	100	64
11	12	PEG	NaOEt	80	100	23
12	12	PEG	Na2CO3	60	100	65
13	12	PEG	Na2CO3	25	100	Trace

^a Reaction conditions: Iodobenzene (1 mmol), phenylboronic acid (1 mmol), base (1.5 mmol), solvent (3 mL), under air atmosphere.

^b Isolated yields.

Table 2. Suzuki coupling reactions of aryl halides with aryl boronic acid catalyzed by BNPs@Cur-Pd nanocatalyst.^a

Entry	Aryl halide	Aryl boronic acid	Time (min)	Yield (%)^b	TON	TOF (h^−1)	Melting point (˚C)
							Found	Reported [Ref.]
1	Iodobenzene	PhB(OH)2	60	96	2232	2232	68	68–70 [35]
2	4-Methylbrombenzene	PhB(OH)2	140	91	2116	906	43–44	44–46 [35]
3	4-Methoxyiodobenzene	PhB(OH)2	100	94	2186	1311	87–88	88–90 [35]
4	4-Nitrobromobenzene	PhB(OH)2	45	94	2186	2914	111–113	112–114 [35]
5	4-Methyliodobenzene	PhB(OH)2	95	95	2209	1395	43–44	44–46 [35]
6	4-Methoxybromobenzene	PhB(OH)2	180	89	2069	689	87–88	88–90 [35]
7	Bromobenzene	PhB(OH)2	95	91	2116	1336	68	68–70 [35]
8	3-Methoxybromobenzene	PhB(OH)2	165	95	2209	803	Colourless liquid	Oil [36]
9	Iodobenzene	3,4-diF-C6H3B(OH)2	85	93	2162	1526	39–40	39–40 [37]
10	4-Nitrobromobenzene	3,4-diF-C6H3B(OH)2	70	96	2232	1913	119–120	119–120 [37]

^a Reaction conditions: Iodobenzene (1 mmol), aryl boronic acid (1 mmol). 12 mg nanocatalyst (0.043 mol% Pd), Na₂CO₃ (1.5 mmol) as a base, PEG as a solvent, Temp. 80 °C.

^b Isolated yields.

Scheme 2. Schematic of the Suzuki coupling mechanism by BNPs@Cur-Pd nanocatalyst.

Table 3. Optimization of the reaction conditions for Stille coupling using BNPs@Cur-Pd as a nanocatalyst.^a

Entry	Catalyst (mg)	Solvent	Base	Temp. (^°C)	Time (min)	Yield (%)^b
1	–	PEG	Na2CO3	80	100	N.R.
2	5	PEG	Na2CO3	80	100	63
3	10	PEG	Na2CO3	80	100	81
4	12	PEG	Na2CO3	80	65	96
5	15	PEG	Na2CO3	80	60	96
6	12	H2O	Na2CO3	80	100	44
7	12	DMF	Na2CO3	80	70	93
8	12	DMSO	Na2CO3	80	60	92
9	12	PEG	KOH	80	100	67
10	12	PEG	Et3N	80	100	60
11	12	PEG	NaOEt	80	100	29
12	12	PEG	Na2CO3	60	100	27
13	12	PEG	Na2CO3	25	100	Trace

^a Reaction conditions: Iodobenzene (1 mmol), triphenyltin chloride (0.5 mmol).

^b Isolated yields.

Table 4. The Stille coupling reactions of aryl halides with Ph₃SnCl catalyzed by BNPs@Cur-Pd^a.

Entry	Aryl halide	Phenylating reagent	Time (min)	Yield (%)^b	TON	TOF (h^−1)	Melting point (˚C)
							Found	Reported [Ref.]
1	Iodobenzene	Ph3SnCl	65	96	2232	2060	68	69–70 [35]
2	4-Methylbromobenzene	Ph3SnCl	165	90	2093	761	43–44	44–46 [35]
3	4-Methoxyiodobenzene	Ph3SnCl	130	90	2093	966	87–88	89–90 [35]
4	4-Nitrobromobenzene	Ph3SnCl	45	95	2209	2945	111–113	112–115 [35]
5	4-Methyliodobenzene	Ph3SnCl	120	94	2186	1093	43–44	45–46 [35]
6	4-Methoxybromobenzene	Ph3SnCl	200	87	2023	607	87–88	87–91 [35]
7	Bromobenzene	Ph3SnCl	105	91	2116	1209	68	68–70 [35]
8	2-Methoxybromobenzene	Ph3SnCl	180	91	2116	705	Colorless liquid	Oil [36]
9	4-Cyanobromobenzene	Ph3SnCl	85	90	2093	1477	84–85	83–85 [38]

^a Isolated yields. Reaction conditions: Aryl halide (1 mmol), triphenyltin chloride (0.5 mmol), 12 mg nanocatalyst (0.043 mol% Pd), Na₂CO₃ as a base, PEG as a solvent, Temp. 80 °C).

^b Isolated yields.

Scheme 3. The proposed mechanism for the Stille coupling with BNPs@Cur-Pd nanocatalyst.

Table 5. Optimization of the reaction conditions for Heck coupling over the BNPs@Cur-Pd catalyst.^a

Entry	Catalyst (mg)	Solvent	Base	Temperature (^oC)	Time (min)	Yield (%)^b
1	–	PEG	Na2CO3	120	100	N.R.
2	12	PEG	Na2CO3	120	80	61
3	16	PEG	Na2CO3	120	45	97
4	20	PEG	Na2CO3	120	35	97
5	16	H2O	Na2CO3	120	100	22
6	16	DMSO	Na2CO3	120	400	85
7	16	DMF	Na2CO3	120	50	97
8	16	PEG	KOH	120	60	48
9	16	PEG	Et3N	120	60	70
10	16	PEG	NaOEt	120	60	15
11	16	PEG	Na2CO3	100	60	69
12	16	PEG	Na2CO3	25 °C	100	Trace

^a Reaction conditions: Iodobenzene (1 mmol), alkene (1.2 mmol).

^b Isolated yields.

Table 6. The Heck coupling reactions for aryl halides with alkenes catalyzed by BNPs@Cur-Pd nanocatalyst.^a

Entry	Aryl halide	alkene	Time (min)	Yield (%)^a	TON	TOF (h^−1)	Melting point (˚C) [Ref.]
1	Iodobenzene	Butyl acrylate	45	97	1672	2229	Oil [39]
2	4-Methyliodobenzene	Butyl acrylate	60	91	1568	1568	Oil [39]
3	4-Methoxyiodobenzene	Butyl acrylate	240	88	1517	379	Oil [39]
4	4-Nitrobromobenzene	Butyl acrylate	260	96	1655	382	60–62 [40]
5	Bromobenzene	Butyl acrylate	300	91	1568	313	Oil [39]
6	4-Methylbromobenzene	Butyl acrylate	360	90	1551	258	Oil [39]
7	4-Methoxybromobenzene	Butyl acrylate	480	90	1551	194	Oil [39]
8	Iodobenzene	Methyl acrylate	50	95	1637	1964	Oil [41]
9	4-Methyliodobenzene	Methyl acrylate	275	90	1551	338	55–57 [42]
10	Iodobenzene	Acrylonitrile	50	96	1655	1986	Oil [43]

^a Reaction conditions: Iodobenzene (1 mmol), alkene chloride (1.2 mmol), 16 mg nanocatalyst (0.058 mol% Pd), Na₂CO₃ as a base, PEG as a solvent, Temp. 120 °C).

^b Isolated yields.

Scheme 4. Schematic of the Heck coupling mechanism by BNPs@Cur-Pd nanocatalyst.

Table 7. Comparing the performance of BNPs@Cur-Pd catalyst with the previously reported procedure in the C–C coupling of iodobenzene and phenylboronic acid.

Entry	Catalyst type	Pd (mol%)	Time (min)	Temp (°C)	Yield (%)	Ref.
1	Polymer anchored Pd (II) Schiff base complex	0.5	300	80	99	[44]
2	Fe3O4/SiO2–DTZ–Pd	0.5	130	60	94	[45]
3	Pd@SBA-15/ILDABCO	0.5	90	80	97	[46]
4	SBA-16-2 N-Pd (II)	0.5	120	60	99	[47]
5	NHC-Pd (II) complex	1	12h	80	88	[41]
6	Pd nanoparticle	1	12h	100	95	[48]
7	CA/Pd (0)	0.5–2	120	100	94	[49]
8	Pd/Au NPs	4	24 h	80	88	[50]
9	Pd (0)-SMTU-boehmite	0.32	75	80	95	[25]
10	Pd(Curcumin)2	5	2–6 h	150	90	[33]
11	BNPs@Cur-Pd	0.043	60	80	96	This work

Figure 9. Reusability performance of BNPs@Cur-Pd in the Suzuki coupling reaction of iodobenzene with phenylboronic acid.

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