Synthesis and application in asymmetric catalysis of P-stereogenic pincer–metal complexes

Xiang, Yijun; Ge, Qianyi; Wu, Shulei; Zheng, Xiaohui; Yang, Zehua

doi:10.1039/d0ra00377h

Cited by 10 publications

(2 citation statements)

References 89 publications

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“…Since then, many other nickel complexes containing unsymmetrical POCN ligands have been described [ 82 ], including various substituted analogues of complex 3a , such as compound 7 ( Figure 4 ) [ 80 ]. Optically active species are also known, for example, a complex containing the imidazole fragment ( 8 and 9 ) ( Figure 4 ), which is successfully used in the asymmetric Suzuki–Miyaura cross-coupling reaction [ 83 , 84 , 85 , 86 ], as well as complex 10 [ 87 ], containing diisopropylphosphinite and imine fragments, which can be oxidized with bromine or N -bromosuccinimide to complex 11 ( Figure 4 ). It is interesting to note that complex 12 also obtained by Zargarian and co-workers, containing the diphenylphosphinite fragment, undergoes two-electron oxidation of the phosphinite fragment with the formation of complex 13 upon interaction with bromine ( Figure 4 ).…”

Section: Pocn Complexesmentioning

confidence: 99%

Recent Advances in Chemistry of Unsymmetrical Phosphorus-Based Pincer Nickel Complexes: From Design to Catalytic Applications

et al. 2021

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Pincer complexes play an important role in organometallic chemistry; in particular, their use as homogeneous catalysts for organic transformations has increased dramatically in recent years. The high catalytic activity of such bis-cyclometallic complexes is associated with the easy tunability of their properties. Moreover, the phosphorus-based unsymmetrical pincers showed higher catalytic activity than the corresponding symmetrical analogues in several catalytic reactions. However, in modern literature, an increasing interest in the development of catalysts based on non-precious metals is observed. For example, nickel, which is an affordable and sustainable analogue of platinum and palladium, known for its low toxicity, has attracted increasing attention in the catalytic chemistry of transition metals in recent years. Thus, this mini-review is devoted to the recent advances in the chemistry of unsymmetrical phosphorus-based pincer nickel complexes, including the ligand design, the synthesis of nickel complexes and their catalytic applications.

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Section: Pocn Complexesmentioning

confidence: 99%

Recent Advances in Chemistry of Unsymmetrical Phosphorus-Based Pincer Nickel Complexes: From Design to Catalytic Applications

et al. 2021

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“…Both mono-and diphosphines found broad applications, especially those with simple design and relatively low cost, like PPh 3 , DPPE, DPPP, and DPPB [18,19], but chiral ones as well, like Chiraphos or atropisomeric BINAP and SEGPHOS, for asymmetric synthesis (Chart 3). Phosphine groups are present on "pincer" ligands of the PCP or PNP type [20] (also in their chiral versions) [21] or in other mixed species, often associated to sulfur or oxygen and nitrogen donors, to afford hemilabile ligands. In fact, phosphorus is a "soft" donor that strongly binds to "soft" metal centres such as Rh(I) ions, while nitrogen and oxygen are relatively "hard" donors and therefore rather labile with this metal ion.…”

Section: Phosphines and Other P-donorsmentioning

confidence: 99%

Rh(I) Complexes in Catalysis: A Five-Year Trend

et al. 2021

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Rhodium is one of the most used metals in catalysis both in laboratory reactions and industrial processes. Despite the extensive exploration on “classical” ligands carried out during the past decades in the field of rhodium-catalyzed reactions, such as phosphines, and other common types of ligands including N-heterocyclic carbenes, ferrocenes, cyclopentadienyl anion and pentamethylcyclopentadienyl derivatives, etc., there is still lively research activity on this topic, with considerable efforts being made toward the synthesis of new preformed rhodium catalysts that can be both efficient and selective. Although the “golden age” of homogeneous catalysis might seem over, there is still plenty of room for improvement, especially from the point of view of a more sustainable chemistry. In this review, temporally restricted to the analysis of literature during the past five years (2015–2020), the latest findings and trends in the synthesis and applications of Rh(I) complexes to catalysis will be presented. From the analysis of the most recent literature, it seems clear that rhodium-catalyzed processes still represent a stimulating challenge for the metalloorganic chemist that is far from being over.

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Palladium/Xiao‐Phos‐Catalyzed Kinetic Resolution of sec‐Phosphine Oxides by P‐Benzylation

2021

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P-stereogenic tert-and sec-phosphines have wide applications in asymmetric catalysis, materials, and pharmaceutical chemistry, however, their practical synthesis still constitutes a significant challenge. Herein, a successful kinetic resolution of rac-secondary phosphine oxides via the enantioselective P-benzylation process catalyzed by the palladium/ Xiao-Phos was designed. Both tert-and sec-phosphine oxides were delivered in good yield and excellent enantiopurity (selectivity factor up to 226.1). The appealing synthetic utilities are further demonstrated by the facile preparation of several valuable P-chiral compounds, precursors of bidentate ligands, as well as transition metal complexes.Scheme 1. Approaches to access to P-stereogenic phosphines.

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Synthesis and application in asymmetric catalysis of P-stereogenic pincer–metal complexes

Abstract: P-stereogenic pincer: synthesis and application in asymmetric catalysis.

Cited by 10 publications

References 89 publications

Recent Advances in Chemistry of Unsymmetrical Phosphorus-Based Pincer Nickel Complexes: From Design to Catalytic Applications

Recent Advances in Chemistry of Unsymmetrical Phosphorus-Based Pincer Nickel Complexes: From Design to Catalytic Applications

Rh(I) Complexes in Catalysis: A Five-Year Trend

Palladium/Xiao‐Phos‐Catalyzed Kinetic Resolution of sec‐Phosphine Oxides by P‐Benzylation

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