北京高压科学研究中心1-己烯的高压固态Alder-Ene反应数据集（2023-2025）

Alder-ene反应是一种发生在烯烃与烯丙基氢之间的化学反应，为构建C–C键提供了高效途径。传统上，该反应通常需要催化剂及高温条件才能进行。在本研究中，我们报道了1-己烯在高压条件下的反应行为。通过高压原位拉曼和红外光谱确定相变与反应阈值。利用气相色谱-质谱（GC-MS）确定产物组成：GC–MS鉴定结果明确显示生成了二聚体产物（7-甲基-4-十一烯和4-十二烯），并通过二甲基二硫（DMDS）衍生化方法进一步确定了二聚产物的结构，进而提出1-己烯在高压下反应的可能路径，为在高压室温条件下实现Alder-ene反应的提供了可行性。利用高压原位中子衍射，确定1-己烯在高压下的结构演化，确定其在高压下的分子堆积形式：原位中子衍射表明反应不遵循拓扑化学规则，原子间的距离远大于反应所需的最小距离，指向晶态内需发生更大幅度的运动才能发生反应。通过反应机理与能垒计算，得到六元环过渡态，其能量在~20 GPa显著降低，阐明“压力降低过渡态能量”的驱动本质，使得反应顺利进行。原位中子衍射在日本J PARC的BL11 PLANET高压中子衍射线站开展，原位光谱实验使用北京高压科学研究中心Renishaw Raman microscope和Bruker VERTEX 70v，质谱分析使用巴黎-爱丁堡压机压缩1-己烯以获得产物PE-20，对PE-20的质谱分析在Agilent Technologies和北京高压科学研究中心进行，理论计算六元环过渡态及其随压力的能量变化计算在北京高压科学研究中心开展，用于机制与动力学可达性论证。通过多证据交叉验证相变/反应阈值（原位中子衍射，原位光谱）、产物组成（GC–MS）、机理能垒（理论）相互印证，提升了结论的可信度。此数据能实现绿色与条件温和的合成反应：在室温、无催化剂条件下实现烯烃Alder Ene 构建C–C键，为避免高温/光化学/金属催化提供替代路径，为地球深部链状烯烃的转化规律提供参考。

The Alder-ene reaction is a chemical reaction occurring between alkenes and allylic hydrogens, providing an efficient pathway for constructing C–C bonds. Traditionally, this reaction typically requires catalysts and high-temperature conditions to proceed. In this study, we report the reaction behavior of 1-hexene under high-pressure conditions. Phase transitions and reaction thresholds were identified using in-situ high-pressure Raman and infrared spectroscopy. The product composition was determined via gas chromatography-mass spectrometry (GC-MS): GC-MS identification clearly showed the formation of dimeric products (7-methyl-4-undecene and 4-dodecene). The structure of the dimeric products was further confirmed using the dimethyl disulfide (DMDS) derivatization method, based on which we propose the possible reaction pathway of 1-hexene under high pressure, demonstrating the feasibility of realizing the Alder-ene reaction under high-pressure and room-temperature conditions. High-pressure in-situ neutron diffraction was employed to determine the structural evolution of 1-hexene under high pressure and its molecular packing pattern under such conditions. In-situ neutron diffraction results indicate that the reaction does not follow topochemical rules: the interatomic distances are much larger than the minimum distance required for the reaction, implying that large-amplitude motions within the crystalline state are necessary for the reaction to occur. Through reaction mechanism and energy barrier calculations, we obtained the six-membered ring transition state, whose energy is significantly reduced at ~20 GPa, clarifying the driving nature of "pressure lowering the transition state energy" which enables the smooth progression of the reaction. The in-situ neutron diffraction experiments were carried out at the BL11 PLANET high-pressure neutron diffraction beamline of the Japan Proton Accelerator Research Complex (J-PARC). The in-situ spectroscopic experiments were conducted using the Renishaw Raman microscope and Bruker VERTEX 70v at the Center for High Pressure Science and Technology Advanced Research (HPSTAR) in Beijing. 1-hexene was compressed using a Paris-Edinburgh press to obtain product PE-20, and GC-MS analysis of PE-20 was performed at Agilent Technologies and HPSTAR Beijing. Theoretical calculations of the six-membered ring transition state and its energy variation with pressure were carried out at HPSTAR Beijing to demonstrate the reaction mechanism and kinetic accessibility. Cross-validation of phase transitions/reaction thresholds (via in-situ neutron diffraction and in-situ spectroscopy), product composition (via GC-MS), and mechanistic energy barriers (via theoretical calculations) mutually corroborate each other, enhancing the reliability of the conclusions. This dataset enables green and mild synthetic reactions: realizing the Alder-ene reaction of alkenes to construct C–C bonds under room-temperature and catalyst-free conditions, providing an alternative pathway to avoid high-temperature, photochemical, or metal-catalyzed reactions, and offering references for the transformation rules of linear alkenes in the deep Earth.