Phosphonium-based aminophosphines as bifunctional ligands for sequential catalysis of one-pot hydroformylation–acetalization of olefins

Abstract

A series of ionic phosphonium-based aminophosphines L1–L3 were prepared and fully characterized, in each of which the involved bifunctional moieties of the phosphine fragment and Lewis acidic phosphonium were linked together by stable chemical bonds and bridged by one N-atom.

Homogeneous hydroformylation of long chain alkenes catalyzed by water soluble phosphine rhodium complex in CH3OH and efficient catalyst cycling

“…The side reactions mainly include 1dodecene isomerization to generate internal dodecenes and 1dodecene hydrogenation to dodecane, and then the acetalation reaction of the formed aldehydes to methylacetals. 33 As presented in Table 1, the solvents and their amounts have great inuence on the hydroformylation of 1-dodecene. Among them, methanol exhibited superior performance to other solvents, the reason might be that the rhodium precursor, ligand TPPTS and 1-dodecene had a better solubility in methanol under the reaction temperature, and thus creating a single phase in which the homogeneous hydroformylation of long chain alkenes proceeded smoothly.…”

Reusable Catalysts for Hydroformylation‐Based Reactions

“…A follow-up study was carried out on the preparation of acetals through sequential hydroformylation/ acetalization, where a series of olefins and polyols were tested using this water-soluble catalytic system. [150] Liu et al [151] developed a series of bifunctional molecules 41-43, which encompass both aminophosphine moiety and Lewis acidic phosphonium group (Figure 24).…”

“…Bifunctional aminophosphine-phosphonium ligands, developed by Liu et al [151] catalyst [Rh(CO) 2 acac]/44 was applied in the hydroformylation/ acetalization of styrene using ethylene glycol as acetalization reagent, leading to full conversion in 7 h, with 97 % selectivity for acetals (Table 2, entry 3). In addition, using a biphasic system composed of [Bmim]BF 4 ionic liquid, the catalyst was recycled and reused in several cycles, presenting a small activity decrease (from 99 to 86 %) along seven consecutive runs.…”

“…Liu et al [151] . developed a series of bifunctional molecules 41–43 , which encompass both aminophosphine moiety and Lewis acidic phosphonium group (Figure 24).…”

Co-catalysis over Bi-functional Ligand Based Ir-catalyst for Tandem Hydroformylation-acetalization Reaction

“…但碱性膦 配体修饰的金属催化剂和酸催化剂在氢甲酰化条件下 自由度较高, 可能造成一定程度上的"酸碱对"的淬灭, 从而影响串联反应进程. 而在同分子共催化体系中, 通 过化学键将过渡金属催化剂和有机酸催化剂相连 [20][21] , 构建双功能催化剂体系, 不仅将两种功能基团有效阻 隔, 实现分子内协同催化作用, 还利于催化剂回收循环 使用. 研究表明, 季鏻鎓[P(V) ＋ ]是典型的 Lewis 酸催化 剂, 通过对羰基化合物的氧原子亲电活化, 有效促进多 种类型反应: 如酮的硅腈化反应 [22] 、羟醛缩合反应 (Aldol reaction) [23] 和 Baylis-Hillman 反应 [24] 等.…”