Interplay of solvent and metal identity determines rates and stereoselectivities in M(IV)-Beta-catalyzed intramolecular Prins cyclization of citronellal

doi:10.1016/S1872-2067(24)60122-1

Abstract

Abstract:

Zeolites of *BEA framework topology containing isomorphously substituted Lewis acidic metal centers catalyze the liquid-phase intramolecular Prins cyclization of citronellal with outstanding catalytic activity and (dia-)stereoselectivity to the commercially most valuable product, isopulegol (IPL). Effects of the metal-center identity and solvent type were occasionally noted, yet without systematic studies hitherto reported. Here, characteristic dependences of catalytic activities and stereoselectivities on solvent and metal identity were uncovered over four M(IV)-Beta catalysts (M = Sn, Ti, Zr and Hf) in four distinct solvents (i.e., acetonitrile, tert-butanol, cyclohexane and n-hexane). Zr- and Hf-Beta were the most active in acetonitrile and the most selective (> 90% to IPL) in tert-butanol, though their activities were generally lower than Ti- and Sn-Beta in solvents other than acetonitrile. By comparison, Ti-Beta was inferior to other catalysts in terms of both activity and IPL selectivity (as previously shown) in acetonitrile but became the most active in other solvents, with markedly increased IPL selectivity from 60% to 70%-80%. Combining multiple site discrimination and quantification techniques, turnover frequencies were determined for the first time in this reaction; such site-based activities, coupled with comprehensive kinetic interrogations, not only enabled a rigorous comparison of catalytic activities across M-Beta catalysts but also provided deeper insights into the free energy driving forces as solvent and metal identity are varied. The activity and selectivity trends, as well as those for the adsorption and intrinsic activation parameters are caused by solvent co-binding at the active site (acetonitrile and tert-butanol) and less quantifiable crowding effects (cyclohexane) due to the limited pore space and the need to accommodate relatively bulky reactant-derived moieties. This work exemplifies how the interplay of metal identity and solvent determines the reactivities and selectivities in Lewis-acid-catalyzed reactions within confined spaces.

Key words: Citronellal, Prins cyclization, Carbonyl-ene reaction, Solid acid, Lewis acidic zeolite, Solvent effect

Shugang Sun, Yang Zhu, Letian Hong, Xuebing Li, Yu Gu, Hui Shi. Interplay of solvent and metal identity determines rates and stereoselectivities in M(IV)-Beta-catalyzed intramolecular Prins cyclization of citronellal[J]. Chinese Journal of Catalysis, 2024, 66: 233-246.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60122-1

https://www.cjcatal.com/EN/Y2024/V66/I11/233

Figures/Tables 11

Scheme 1. Intramolecular Prins cyclization of (+)-citronellal, with the most useful stereoisomer (-)-isopulegol and its subsequent hydrogenation product (-)-menthol highlighted in red.

Table 1 Textural properties, elemental composition, acid site/active site quantification data and relative densities of hydrogen-bonded silanols for the studied M-Beta samples.

Sample	S_BET (m² g⁻¹)	Total pore volume (cm³ g⁻¹)	Micropore volume (cm³ g⁻¹)	Si/M ^a	Active sites ^b (μmol g⁻¹)	Acid sites ^c		Φ_IR^d
Sample	S_BET (m² g⁻¹)	Total pore volume (cm³ g⁻¹)	Micropore volume (cm³ g⁻¹)	Si/M ^a	Active sites ^b (μmol g⁻¹)	Lewis acidity (μmol g⁻¹)	Brønsted acidity (μmol g⁻¹)	Φ_IR^d
Ti-Beta	583	0.31	0.21	97	47	119	n.d.^e	0.13
Zr-Beta	590	0.34	0.21	51	122	214	n.d.^e	0.18
Hf-Beta	577	0.31	0.21	106	38	100	n.d.^e	0.19
Sn-Beta	536	0.35	0.19	251	51	50	n.d.^e	0.17

Fig. 1. IR spectra of adsorbed pyridine (upon saturation of surface acid sites and evacuation to remove gaseous or physisorbed pyridine) on dehydrated M-Beta samples (a) and freshly activated M-Beta samples (b). All spectra have been normalized against the ν(Si?O?Si) overtone at 1870 cm?1, assumed to have an identical molar extinction coefficient for all samples. Spectra are vertically offset for clarity.

Table 2 Cyclization reactions of (±) citronellal on M-Beta catalysts in three distinct solvents a.

Catalyst	Solvent	Conv. (%)	Yield_pulegol^b (%)	Sel._pulegol^b (%)	Stereosel._IPL^c (%)
Ti-Beta	acetonitrile	26.8	26.3	98.1	60
Zr-Beta	acetonitrile	98.9	97.6	98.7	84
Hf-Beta	acetonitrile	96.2	96.2	100	85
Sn-Beta	acetonitrile	97.6	95.3	97.6	78
Ti-Beta	cyclohexane	99.9	98.4	98.5	74
Zr-Beta	cyclohexane	98.4	97.6	99.2	87
Hf-Beta	cyclohexane	99.7	99.7	100	83
Sn-Beta	cyclohexane	97.5	97.1	99.5	71
Ti-Beta	tert-Butanol	98.5	93.1	94.5	80
Zr-Beta	tert-Butanol	94.4	94.4	100	91
Hf-Beta	tert-Butanol	98.3	98.3	100	91
Sn-Beta	tert-Butanol	98.4	98.4	100	90

Fig. 2. Conversion of citronellal (filled circles, left ordinate) and diastereoselectivity to isopulegol (IPL, empty triangles, right ordinate) over M-Beta catalysts in acetonitrile (a), cyclohexane (b) and tert-butanol (c). Reaction conditions: 1.0 g of (±) citronellal, 60 mL solvent, 250 mg of catalyst, 1000 r min?1, 333 K. Dashed lines only represent trends.

Fig. 3. Turnover frequencies of citronellal cyclization over M-Beta in different solvents under a given set of conditions (0.11 mol L?1 and 333 K).

Fig. 4. Turnover rates (normalized to the active site densities determined by in situ titration) for (±)-citronellal conversion as a function of its concentration over M-Beta catalysts in acetonitrile (a), tert-butanol (b), cyclohexane (c) and n-hexane (d) at 333 K. The lines represent the regressed best fits to Eq. (1).

Table 3 Regressed kinetic and thermodynamic parameters (to Eq. (1)) from the reaction data measured (shown in Fig. 4) over M-Beta catalysts in different solvents at 333 K.

Solvent	Catalyst	K_ads (L mol^-1)	k_cyc ^a (mol_CIT/IPL mol_LAS min^-1)
Acetonitrile	Ti-Beta	16±6 (11±2)	4±1 (4±2)
	Zr-Beta	10±2 (7±1)	60±3 (53±3)
	Hf-Beta	6±3 (6±3)	215±64 (178±48)
	Sn-Beta	49±9 (50±10)	35±2 (25±1)
tert-Butanol	Ti-Beta	4±0.4 (5±0.3)	140±5 (100±2)
	Zr-Beta	10±2 (11±2)	33±2 (30±2)
	Hf-Beta	26±9 (35±10)	37±3 (32±2)
	Sn-Beta	17±5 (19±5)	40±3 (36±2)
Cyclohexane	Ti-Beta	2±0.5 (4±1)	79 ±14 (36±5)
	Zr-Beta	48±8 (57±17)	4±0.2 (3±0.2)
	Hf-Beta	22±6 (20±6)	7±0.5 (6±0.5)
	Sn-Beta	3±1 (5±2)	15±5 (7±1)
n-Hexane	Ti-Beta	91±19 (99±20)	101±5 (72±4)
	Zr-Beta	49±10 (47±10)	41±2 (35±2)
	Hf-Beta	63±5 (49±15)	99±2 (94±7)
	Sn-Beta	48±29 (54±32)	71±11 (50±7)

Fig. 5. Ratio of the first-order rate constant (Kadskcyc in Eq. (1)) in a given solvent relative to that in n-hexane (a) and corresponding differences in the free energy of activation (at 333 K) in the first-order kinetic regime between each solvent and n-hexane (b).

Fig. 6. Ratio of the zero-order rate constant (kcyc in Eq. (1)) in a given solvent relative to that in n-hexane (a) and corresponding differences in the intrinsic free energy of activation (ΔGint? at 333 K) between each solvent and n-hexane (b).

Scheme 2. Proposed elementary steps for citronellal (CIT) cyclization to isopulegol (IPL) over M-Beta catalysts in different solvents. Black arrows denote steps that occur on sites not covered with solvent molecules (as in the case of n-hexane and cyclohexane), green arrows denote steps that occur on sites where acetonitrile (ACN) is (co-)adsorbed, and blue arrows denote steps that occur on sites where tert-butanol (TBO) is (co-)adsorbed. Bidirectional arrows with an oval on top indicate quasi-equilibrated steps with the designated equilibrium constants, whereas unidirectional arrows with a ‘?’ symbol indicate the kinetically relevant step in each catalytic cycle (black, blue and green).

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