Construction of P‐Chiral Alkenylphosphine Oxides through Highly Chemo‐, Regio‐, and Enantioselective Hydrophosphinylation of Alkynes

Zhang, Junliang; Dai, Qiang; Liu, Lu; Qian, Yanyan; Li, Wenbo

doi:10.1002/ange.202009358

Cited by 18 publications

(3 citation statements)

References 65 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Meanwhile, the enantioenriched P‐chiral SPOs can be readily transformed to diverse P‐chiral TPOs. Accordingly, exploring KR has been devoted in the elegant works on the catalytic enantioselective construction of P‐chiral TPOs from SPOs [11a,c–h, 12] . However, owing to the elusive degree of racemization of SPOs in most of these catalytic systems, the success examples are scarce, [12] and a common platform to achieving KR of both alkyl‐aryl‐ and diaryl‐based SPOs is still unmet.…”

Section: Resultsmentioning

confidence: 99%

“…To secure the excellent yield and enantioselectivity, the preparation of P‐chiral TPOs generally requires an excess amount of SPOs (≥2.0 equivalents), [11a,c–h, 12] which is ascribed to the high interconversion energy between their ( S )‐ and ( R )‐enantiomers. As such, chemists also attempted to leverage this feature to attain kinetic resolution (KR) of SPOs, to synthesize P‐chiral TPOs and SPOs simultaneously in one single enantioselective transformation.…”

Section: Resultsmentioning

confidence: 99%

“…However, changing the 2,4,6‐disubstituted aryls to other aryls with less steric hindrance were also attempted with ee values less than 60 %, likely due to the insufficient enantiofacial differentiation caused by similar steric effect from the two aryl‐ groups. Nevertheless, it is worth mentioning that this is the first general system to render P‐chiral tertiary phosphine oxides with high yields and ees from both alkyl‐aryl‐ and diaryl‐substituted SPOs as the feedstocks [11d] …”

Section: Resultsmentioning

confidence: 99%

See 2 more Smart Citations

Catalytic Asymmetric Hydrophosphinylation of 2‐Vinylazaarenes to Access P‐Chiral 2‐Azaaryl‐Ethylphosphine Oxides

et al. 2023

View full text Add to dashboard Cite

A chiral Brønsted acid-catalysed asymmetric hydrophosphinylation of 2-vinylazaarenes by secondary phosphine oxides is described. A variety of P-chiral 2azaaryl-ethylphosphine oxides are synthesized with high yields and ees, of which both the substituents of phosphines and azaarenes can be flexibly modulated, underscoring an exceptionally broad scope of substrates. These adducts are valuable to asymmetric metal catalysis since the resultant P-chiral tertiary phosphines from the reduction of them are verified as a kind of effective C 1 -symmetric chiral 1,5-hybrid P,N-ligands. Importantly, this catalysis platform enables the generic and efficient kinetic resolution of P-chiral secondary phosphine oxides. It thus provides an expedient approach to access the enantiomers of the P-chiral tertiary phosphine oxides derived from asymmetric hydrophosphinylation, further improving the utility of the method.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Catalytic Asymmetric Hydrophosphinylation of 2‐Vinylazaarenes to Access P‐Chiral 2‐Azaaryl‐Ethylphosphine Oxides

et al. 2023

View full text Add to dashboard Cite

show abstract

Cobalt‐Catalysed Asymmetric Addition and Alkylation of Secondary Phosphine Oxides for the Synthesis of P‐Stereogenic Compounds

Weng

Cheng

et al. 2021

Angewandte Chemie

View full text Add to dashboard Cite

The catalytic asymmetric synthesis of P-chiral phosphorus compounds is an important way to construct Pchiral ligands. Herein, we report a new strategy that adopts the pyridinyl moiety as the coordinating group in the cobaltcatalysed asymmetric nucleophilic addition/alkylation of secondary phosphine oxides. A series of tertiary phosphine oxides were generated with up to 99 % yield and 99.5 % ee, and with broad functional-group tolerance. Mechanistic studies reveal that (R)-secondary phosphine oxides preferentially interact with the cobalt catalysts to produce P-stereogenic compounds.Chiral phosphorus compounds play important roles as ligands [1] or organic catalysts [2] in asymmetric catalysis. Compared to the synthesis of axial-, planar-, and carboncentered chiral phosphorus compounds, the synthesis of Pstereogenic phosphines has been less investigated. The main recent strategies for the preparation of P-chiral compounds involve the use of chiral auxiliary materials or the resolution of racemates. [3] These classical methods require stoichiometric chiral agents or generate an equivalent amount of compound with an opposite configuration. [4] Recently, several asymmetric catalytic methods were developed based on the desymmetrization of phosphine oxides via CÀH bond activation, [5] asymmetric addition, [6] ring-closing metatheses, [7] and [2+2+2] cycloaddition processes. [8] In addition, secondary phosphines have been used as nucleophiles in asymmetric conjugate addition, [9] alkylation, [10] and arylation reactions. [11] However, in this process, the strong coordination ability of the secondary phosphines may lead to deactivation of the metal catalyst, thereby reducing the enantioselectivity. Therefore, the development of alternative methods for the synthesis of P-chiral compounds is still highly necessary.Compared with secondary phosphines, secondary phosphine oxides (SPOs) are more stable in air and have low toxicity to metal catalysts. Nonetheless, only a few synthetic examples have been reported for the preparation of optically active tertiary phosphine oxides (TPOs) from SPOs. In 2016, Gaunt and co-workers reported a new strategy in which Cu combined with chiral pyridine-2,6-bis(oxazolines) ligand (pybox) was applied for the enantioselective arylation of SPOs with diaryliodonium salt, affording P-chiral tertiary phosphorus compounds with up to 98 % ee (Scheme 1 a). [12] The Cai group reported a Pd-catalysed arylation of SPOs with aryl iodides with moderate to high ee (Scheme 1 b). [13] Recently, Zhang and co-workers also reported Pd-catalysed asymmetric arylation and alkenylation reactions of SPOs (Scheme 1 c), in which products were obtained in up to 99 % ee. [14] In addition to the above examples, the Qing-Wei Zhang group developed a Ni-catalysed kinetic resolution of SPOs via an allylic substitution process, providing a series of Pstereogenic compounds with high enantioselectivity (Scheme 1 d). [15] However, the SPOs in the abovementioned examples usually contain one aryl and one alkyl group. Substrates b...

show abstract

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

2021

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Construction of P‐Chiral Alkenylphosphine Oxides through Highly Chemo‐, Regio‐, and Enantioselective Hydrophosphinylation of Alkynes

Cited by 18 publications

References 65 publications

Catalytic Asymmetric Hydrophosphinylation of 2‐Vinylazaarenes to Access P‐Chiral 2‐Azaaryl‐Ethylphosphine Oxides

Catalytic Asymmetric Hydrophosphinylation of 2‐Vinylazaarenes to Access P‐Chiral 2‐Azaaryl‐Ethylphosphine Oxides

Cobalt‐Catalysed Asymmetric Addition and Alkylation of Secondary Phosphine Oxides for the Synthesis of P‐Stereogenic Compounds

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

Contact Info

Product

Resources

About