M(IV)-Beta分子筛催化香茅醛分子内Prins环化: 溶剂与金属中心共同决定活性及立体选择性

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

催化学报 ›› 2024, Vol. 66: 233-246.DOI: 10.1016/S1872-2067(24)60122-1

M(IV)-Beta分子筛催化香茅醛分子内Prins环化: 溶剂与金属中心共同决定活性及立体选择性

孙书钢^a^,¹, 朱洋^a^,¹, 洪乐天^a, 李学兵^b, 顾宇^a^,^*(), 施慧^a^,^*()

^a扬州大学化学化工学院, 江苏扬州 225009
^b宁波工程学院, 材料与化学工程学院, 浙江宁波 315211

收稿日期:2024-07-25 接受日期:2024-08-27 出版日期:2024-11-18 发布日期:2024-11-10
通讯作者: *电子信箱: guyu@yzu.edu.cn (顾宇),shihui@yzu.edu.cn (施慧).
作者简介:¹共同第一作者.
基金资助:
国家自然科学基金(22072128);国家自然科学基金(22179134);国家自然科学基金(22308301)

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

Shugang Sun^a^,¹, Yang Zhu^a^,¹, Letian Hong^a, Xuebing Li^b, Yu Gu^a^,^*(), Hui Shi^a^,^*()

^aSchool of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225009, Jiangsu, China
^bSchool of Materials and Chemical Engineering, Ningbo University of Technology, Ningbo 315211, Zhejiang, China

Received:2024-07-25 Accepted:2024-08-27 Online:2024-11-18 Published:2024-11-10
Contact: *E-mail: guyu@yzu.edu.cn (Y. Gu),shihui@yzu.edu.cn (H. Shi).
About author:¹Contributed equally to this work.
Supported by:
National Natural Science Foundation(22072128);National Natural Science Foundation(22179134);National Natural Science Foundation(22308301)

摘要/Abstract

摘要：

右旋香茅醛经历分子内Prins环化, 可生成左旋异蒲勒醇(IPL), 其加氢产物L-薄荷醇具有很高的经济价值. 具有Lewis酸性金属中心的BEA型分子筛(M-Beta)对香茅醛Prins环化反应表现出优异的活性和蒲勒醇化学选择性, 以及较高的IPL立体选择性. 然而, 有关金属中心和溶剂类型对这类材料在该反应中催化性能的影响尚缺乏系统研究. 本文通过考察除金属中心类型外其他性质类似的四种M(IV)-Beta (M = Sn, Ti, Zr, Hf)催化剂以及四种分子尺寸和极性各异的溶剂(乙腈、叔丁醇、环己烷及正己烷)影响, 阐明了催化活性和立体选择性对于金属中心和溶剂类型的依赖关系.

Ti-Beta在乙腈溶剂中活性和IPL选择性最低, 与以往报道一致, 但本工作发现Ti-Beta在叔丁醇、环己烷、正己烷溶剂中活性均高于其他三种M-Beta催化剂; 此外, Ti-Beta上的IPL立体选择性在三种溶剂中相较乙腈溶剂也大大提升(从60%增至70%-80%). Zr-Beta和Hf-Beta在乙腈溶剂中活性最高, 在叔丁醇中IPL立体选择性最高(> 90%), 但在除乙腈外的溶剂中两者活性普遍低于Ti-和Sn-Beta. 通过吡啶、氘代乙腈蒸气吸附的红外光谱, 结合环己胺在反应条件下原位滴定的策略, 测定出该反应的转化频率, 从而详细比较M-Beta催化剂的本征活性. 动力学拟合分析进一步得出各催化剂和溶剂体系中香茅醛吸附的平衡常数和环化决速步的本征速率常数, 并量化了反应自由能驱动力在不同金属中心和溶剂中的差异. 催化活性和关键动力学/热力学参数(本征速率常数和吸附平衡常数)结果表明, 不同溶剂中M-Beta的活性顺序截然不同, 从而否定了金属中心Lewis酸强度作为反应性唯一描述符的猜想. 此外, 四种M-Beta的本征速率常数体现出不同幅度的溶剂效应, 其中Sn-Beta受溶剂性质的影响明显小于其他三种催化剂. 对不同M-Beta逐一分析表明, 在最常用的乙腈溶剂中, Ti-Beta上环化过渡态的能量最高, Hf-Beta的活化Gibbs自由能最低; 在其他溶剂中, Ti-Beta上的活化自由能最低. 乙腈溶剂中Ti-Beta的本征活化焓最高(59 ± 9 kJ mol^-1), Zr-和Hf-Beta上最低(38-44 kJ mol^-1). 相反, 各非对映异构体的立体选择性主要受活化熵而非活化焓控制. 综上可知, 反应活性、选择性以及吸附/本征自由能的变化趋势由溶剂在活性中心的共吸附(乙腈及叔丁醇)以及亚纳米限域空间的位阻效应(环己烷)共同决定.

综上, 本文以香茅醛环化为例, 揭示了在孔道限域环境内, 金属活性中心与溶剂间的相互作用对于Lewis酸催化反应的活性和选择性的多重影响, 为该类催化反应体系的理性设计提供参考.

关键词: 香茅醛, Prins环化, 羰基-烯反应, 固体酸, Lewis酸分子筛, 溶剂效应

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

孙书钢, 朱洋, 洪乐天, 李学兵, 顾宇, 施慧. M(IV)-Beta分子筛催化香茅醛分子内Prins环化: 溶剂与金属中心共同决定活性及立体选择性[J]. 催化学报, 2024, 66: 233-246.

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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图/表 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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M(IV)-Beta分子筛催化香茅醛分子内Prins环化: 溶剂与金属中心共同决定活性及立体选择性

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

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