cas 15754-51-5, Bis(4-methoxyphenyl)phosphine oxide

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Electrochemical Oxidative C–H Phosphonylation of thiazole derivatives in ambient conditions
We herein report a direct electrochemical dehydrogenative C–H phosphonylation of thiazoles derivatives with H2 evolution. Employing electricity as the green and sole oxidant, cheap metal as electrode, the anodic oxidation together with cathodic hydrogen evolution process provides a green and efficient strategy for C–H phosphonylation. A diverse range of phosphorus products were constructed under external metal and oxidant-free conditions at ambient temperature, featuring atom economy, simple operation and wide reaction scope.
Li, Yang,Wu, Lei,Yang, Yan-Tong,Zhu, Jie,Zhu, Peng-Wei
(2021/12/07)

Microwave-Assisted Ruthenium- and Rhodium-Catalyzed Couplings of α-Amino Acid Ester-Derived Phosphinamides with Alkynes
Two different types of new phosphinamide α-amino ester derivatives have been prepared in moderate to high yields via ruthenium(II) and rhodium(III)-catalyzed ortho-C?H functionalization under microwave irradiation. Specifically, the ortho-alkenylated phosphinamides were produced through coupling of phosphinamides containing an α-substituted or α,α-disubstituted α-amino ester with internal alkynes under ruthenium catalysis. In contrast, Ru and the more effective Rh-catalyzed coupling of the α-unsubstituted glycine ester phosphinamide with alkynes resulted in formation of oxidative annulation products, phosphaisoquinolin-1-ones. The developed methods feature the use of easily accessible starting materials, short reaction time, exclusive E-stereoselectivity (for ortho-alkenylation) and good functional group tolerance. The alkenylation reaction was readily scaled up to gram scale. Furthermore, the obtained alkenylated phosphinamide could be transformed into P-containing dipeptides through hydrolysis of the ester group in the catalysis product and subsequent condensation with an α-amino ester.
Li, Xue-Hong,Gong, Jun-Fang,Song, Mao-Ping
supporting information

(2021/12/23)

B(C6F5)3-catalyzed O-H insertion reactions of diazoalkanes with phosphinic acids
A highly efficient base-, metal-, and oxidant-free catalytic O-H insertion reaction of diazoalkanes and phosphinic acids in the presence of B(C6F5)3has been developed. This powerful methodology provides a green approach towards the synthesis of a broad spectrum of α-phosphoryloxy carbonyl compounds with good to excellent yields (up to 99% yield). The protocol features the advantages of operational simplicity, high atom economy, practicality, easy scalability and environmental friendliness.
Jiang, Jun,Zhang, Xinzhi,Zhang, Yangyang,Zhao, Jincheng
supporting information
p. 5772 - 5776
(2021/07/12)

Organic photoredox catalytic α-C(sp3)-H phosphorylation of saturated: Aza -heterocycles
A metal-free C(sp3)-H phosphorylation of saturated aza-heterocycles via the merger of organic photoredox and Br?nsted acid catalyses was established under mild conditions. This protocol provided straightforward and economic access to a variety of valuable α-phosphoryl cyclic amines by using commercially available diarylphosphine oxide reagents. In addition, the D-A fluorescent molecule DCQ was used for the first time as a photocatalyst and exhibited an excellent photoredox catalytic efficiency in this transformation. A series of mechanistic experiments and DFT calculations demonstrated that this transformation underwent a sequential visible light photoredox catalytic oxidation/nucleophilic addition process.
Yi, Ming-Jun,Xiao, Teng-Fei,Li, Wen-Hui,Zhang, Yi-Fan,Yan, Pen-Ji,Zhang, Baoxin,Xu, Peng-Fei,Xu, Guo-Qiang
supporting information
p. 13158 - 13161
(2021/12/16)

Asymmetric Catalytic Approach to Multilayer 3D Chirality
The first asymmetric catalytic approach to multilayer 3D chirality has been achieved by using Suzuki-Miyaura cross-couplings. New chiral catalysts were designed and screened under various catalytic systems that proved chiral amide-phosphines to be more efficient ligands than other candidates. The multilayer 3D framework was unambiguously determined by X-ray structural analysis showing a parallel pattern of three layers consisting of top, middle and bottom aromatic rings. The X-ray structure of a catalyst complex, dichloride complex of Pd-phosphine amide, was obtained revealing an interesting asymmetric environment nearby the Pd metal center. Three rings of multilayer 3D products can be readily changed by varying aromatic ring-anchored starting materials. The resulting multilayer products displayed strong luminescence under UV irradiation and strong aggregation-induced emission (AIE). In the future, this work would benefit not only the field of asymmetric synthesis but also materials science, in particular polarized organic electronics, optoelectronics and photovoltaics.
Wu, Guanzhao,Liu, Yangxue,Rouh, Hossein,Ma, Liulei,Tang, Yao,Zhang, Sai,Zhou, Peng,Wang, Jia-Ying,Jin, Shengzhou,Unruh, Daniel,Surowiec, Kazimierz,Ma, Yanzhang,Li, Guigen
supporting information
p. 8013 - 8020
(2021/05/10)

The organocatalytic enantiodivergent fluorination of β-ketodiaryl-phosphine oxides for the construction of carbon-fluorine quaternary stereocenters
Commercially available cinchona alkaloids that can catalyze the enantiodivergent fluorination of β-ketodiarylphosphine oxides were developed to construct carbon-fluorine quaternary stereocenters. This protocol features a wide scope of substrates and excellent enantioselectivities, and it is scalable.
Xie, Shaolei,He, Zhi-Juan,Zhang, Ling-Hui,Huang, Bo-Lun,Chen, Xiao-Wei,Zhan, Zong-Song,Zhang, Fu-Min
supporting information
p. 2069 - 2072
(2021/03/01)

Enantiodivergent Kinetic Resolution of 1,1′-Biaryl-2,2′-Diols and Amino Alcohols by Dipeptide-Phosphonium Salt Catalysis Inspired by the Atherton–Todd Reaction
A highly enantiodivergent organocatalytic method is disclosed for the synthesis of atropisomeric biaryls via kinetic resolution inspired by a dipeptide-phosphonium salt-catalyzed Atherton–Todd (A-T) reaction. This flexible approach led to both R- and S-enantiomers by fine-tuning of bifunctional phosphonium with excellent selectivity factors (s) of up to 1057 and 525, respectively. The potential of newly synthesized O-phosphorylated biaryl diols was illustrated by the synthesis of axially chiral organophosphorus compounds. Mechanistic investigations suggest that the bifunctional phosphonium halide catalyst differentiates between the in-situ-generated P-species in the A-T process, mainly involving phosphoryl chloride and phosphoric anhydride, thus leading to highly enantiodivergent O-phosphorylation reactions. Furthermore hydrogen bonding interactions between the catalysts and phosphorus molecules were crucial in asymmetric induction.
Chen, Yuan,Fang, Siqiang,Pan, Jianke,Ren, Xiaoyu,Tan, Jian-Ping,Wang, Tianli,Zhang, Hongkui
supporting information
p. 14921 - 14930
(2021/05/10)

Highly Enantioselective Synthesis of Phosphorus-Containing ?-Benzosultams by Bifunctional Phosphonium Salt-Promoted Hydrophosphonylation
?-Benzosultam derivatives are potential drug candidates with diverse biological activities. A series of chiral ?-benzosultams bearing phosphorus functionalities was synthesized by catalytic asymmetric hydrophosphonylation in the presence of a bifunctional phosphonium salt catalyst. The desired hydrophosphonylation products were obtained in good yields with high enantioselectivities, and scale-up reactions and further derivations were successfully accomplished. Some control experiments were also conducted to elucidate the plausible reaction mechanism of this chemical transformation.
Zhang, Song,Feng, Zhenghuai,Jiang, Chunhui,Yu, Xiaojun,Pan, Jianke,Du, Juan,Jiang, Zhiyu,Chen, Yuan,Wang, Tianli
supporting information
p. 11285 - 11290
(2021/07/02)

Manganese-Promoted Regioselective Direct C3-Phosphinoylation of 2-Pyridones
A highly efficient and regioselective manganese-induced radical oxidative direct C?P bond formation between 2-pyridones and secondary phosphine oxides was developed. The C3-selective phosphinoylation was conveniently achieved through a combination of substoichiometric manganese and persulfate oxidant under mild conditions. Various 3-phosphinoylated pyridone products can be obtained in moderate to high yields. Preliminary mechanistic studies suggest that the reaction is likely to involve a radical pathway induced by catalytically active Mn3+ species.
Chantarojsiri, Teera,Kittikool, Tanakorn,Phakdeeyothin, Kunita,Yotphan, Sirilata
supporting information
p. 3071 - 3078
(2021/07/22)

Twofold C?H Activation-Based Enantio- and Diastereoselective C?H Arylation Using Diarylacetylenes as Rare Arylating Reagents
C?H bond activation has been established as an attractive strategy to access axially chiral biaryls, and the most straightforward method is direct C?H arylation of arenes. However, the arylating source has been limited to several classes of reactive and bulky reagents. Reported herein is rhodium-catalyzed 1:2 coupling of diarylphosphinic amides and diarylacetylenes for enantio- and diastereoselective construction of biaryls with both central and axial chirality. This twofold C?H activation reaction stays contrast to the previously explored Miura–Satoh type 1:2 coupling of arenes and alkynes in terms of chemoselectivity and proceeded under mild conditions with the alkyne acting as a rare arylating reagent. Both C?H activation events are stereo-determining and are under catalyst control, with the 2nd C?H activation being diastereo-determining in a remote fashion. Analysis of the stereochemistry of the major and side products suggests moderate enantioselectivity of the initial C?H activation–desymmetrization process. However, the minor (R) rhodium vinyl intermediate is consumed more readily in undesired protonolysis, eventually resulting in high enantio- and diastereoselectivity of the major product.
Hu, Panjie,Kong, Lingheng,Li, Xingwei,Wang, Fen,Zhu, Xiaolin
supporting information
p. 20424 - 20429
(2021/08/09)

Palladium-Catalyzed Phosphoryl-Carbamoylation of Alkenes: Construction of Nonbenzylic C(sp3)?P(O)R2 Bonds via C(sp3)?Pd(II)?P(O)R2 Reductive Elimination
We report the first example of palladium-catalyzed phosphoryl-carbamoylation of alkene-tethered carbamoyl chlorides with P(O)H compounds. Both H-phosphinates and secondary phosphine oxides are compatible with this reaction. DPE-Phos was used as ligand to facilitate nonbenzylic C(sp3)?P bonds formations via C(sp3)?Pd(II)?P reductive elimination. By using this protocol, a range of phosphorylated oxindoles and lactams were obtained in moderate to good yields. (Figure presented.).
Chen, Chen,Sun, Wan,Yan, Yan,Yang, Fang,Wang, Yuebo,Zhu, Yan-Ping,Liu, Liying,Zhu, Bolin
supporting information
p. 2970 - 2975
(2020/07/06)

Cobaloxime Catalysis for Enamine Phosphorylation with Hydrogen Evolution
Direct phosphorylation of enamine and enamide with hydrogen evolution was realized via cobaloxime catalysis under visible-light irradiation. Control experiments and spectroscopic studies demonstrated a reductive quenching pathway of cobaloxime catalyst to produce phosphinoyl radical, which underwent cross-coupling with various enamines (and enamides) to give diverse β-phosphinoyl products in good to excellent yields. More interestingly, Z/E mixture of acyclic enamines could convert into single Z-products with good reactivity.
Lei, Tao,Liang, Ge,Cheng, Yuan-Yuan,Chen, Bin,Tung, Chen-Ho,Wu, Li-Zhu
supporting information
p. 5385 - 5389
(2020/07/08)

Practical Synthesis of Phosphinic Amides/Phosphoramidates through Catalytic Oxidative Coupling of Amines and P(O)?H Compounds
Herein, we report a highly efficient ZnI2-triggered oxidative cross-coupling reaction of P(O)?H compounds and amines. This operationally simple protocol provides unprecedented generic access to phosphinic amides/phosphoramidate derivatives in good yields and short reaction time. Besides, the reaction proceeds under mild conditions, which avoids the use of hazardous reagents, and is applicable to scale-up syntheses as well as late-stage functionalization of drug molecules. The stereospecific coupling is also achieved from readily available optically enriched P(O)?H compounds.
Tan, Chen,Liu, Xinyuan,Jia, Huanxin,Zhao, Xiaowen,Chen, Jian,Wang, Zhiyong,Tan, Jiajing
supporting information
p. 881 - 887
(2020/01/02)

Ru(II)-Catalyzed Amination of Aryl Fluorides via η6-Coordination
We developed a Ru/hemilabile-ligand-catalyzed nucleophilic aromatic substitution (SNAr) of aryl fluorides as the limiting reagents. Significant ligand enhancement was demonstrated by the engagement of both electron-rich and neutral arenes in the SNAr amination without using excess arenes. Preliminary mechanistic studies revealed that the nucleophilic substitution proceeds on a η6-complex of the Ru catalyst and the substrate, and the hemilabile ligand facilitates dissociation of products from the metal center.
Kang, Qi-Kai,Li, Yuntong,Lin, Yunzhi,Shi, Hang
supporting information
p. 3706 - 3711
(2020/03/11)

Electrochemical Oxidative Dehydrogenative Phosphorylation of N-Heterocycles with P(O)-H Compounds in Imidazolium-Based Ionic Liquid
We report a direct and green electrochemical oxidative cross-dehydrogenative coupling reaction of N-heterocycles with hydrogen phosphoryl compounds under external oxidant-free conditions. Various phosphorylation products of substituted carbazoles and indoles are assembled in modest to excellent yields. A hydrogen release process is preliminarily demonstrated and H2 is the sole byproduct. An imidazolium based ionic liquid is selected as the optimal electrolyte.
Dong, Xiaojuan,Jin, Weiwei,Liu, Chenjiang,Wang, Ruige
supporting information

(2020/04/20)

Visible-light-driven metal-free aerobic synthesis of highly diastereoselective phosphinoylpyrroloindoles
A visible-light-driven metal-free phosphorus radical mediated construction of 2-phosphinoyl-3H-pyrrolo[1,2,a]indoles is described. This mild tandem phosphinoylation/cyclization protocol utilizes air as a green oxidant and proceeds in a short span of time at room temperature with high functional group tolerance, and excellent chemo- A nd diastereoselectivity.
Gorre, Ramesh,Enagandhula, Damodar,Balasubramanian, Sridhar,Akondi, Srirama Murthy
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p. 1354 - 1358
(2020/03/03)

Copper mediated C(sp2)-H amination and hydroxylation of phosphinamides
Copper mediated C(sp2)-H amination and hydroxylation of arylphosphinic acid are accomplished by adopting phosphinamide as the directing group. This method is distinguished by its wide substrate scope and excellent functional group tolerance, th
Sun, Shang-Zheng,Shang, Ming,Xu, Hui,Cheng, Tai-Jin,Li, Ming-Hong,Dai, Hui-Xiong
supporting information
p. 1444 - 1447
(2020/02/11)

Catalytic Deoxygenative Coupling of Aromatic Esters with Organophosphorus Compounds
We have developed a deoxygenative coupling of aromatic esters with diarylphosphine oxides/dialkyl phosphonates under palladium catalysis. In this reaction, aromatic esters can work as novel benzylation reagents to give the corresponding benzylic phosphorus compounds. The key of this reaction is the use of phenyl esters, an electron-rich diphosphine as a ligand, and sodium formate as a hydrogen source. Arylcarboxylic acids were also applicable in this reaction using (Boc)2O as an additive. Palladium/dcype worked to activate the acyl C-O bond of the ester and to support the reduction with sodium formate.
Kurosawa, Miki B.,Isshiki, Ryota,Muto, Kei,Yamaguchi, Junichiro
supporting information
p. 7386 - 7392
(2020/04/30)

Transition Metal-Free Synthesis of α-Aminophosphine Oxides through C(sp3)?P Coupling of 2-Azaallyls
Radical reactions have been widely applied in C?P bond-forming strategies. Most of these strategies require initiators, transition metal catalysts, or organometallic reagents. Herein, a transition metal-free C(sp3)?P bond formation to prepare α
Wang, Jing,Deng, Guogang,Liu, Chunxiang,Chen, Zhuo,Yu, Kaili,Chen, Wen,Zhang, Hongbin,Yang, Xiaodong
supporting information
p. 2268 - 2273
(2020/03/04)

Copper-Catalyzed Oxidative C(sp3)?H/N?H Cross-Coupling of Hydrocarbons with P(O)?NH Compounds: the Accelerating Effect Induced by Carboxylic Acid Coproduct
An chelation-assisted oxidative C(sp3)?H/N?H cross coupling of hydrocarbons with P(O)?NH compounds using copper acetate as catalyst is described. The results of kinetic experiments, mechanistic studies and DFT calculations demonstrate the importance of acetic acid coproduct as an additive for promoting the formation of intermediate bis((diphenylphosphoryl)(quinolin-8-yl)amino)copper (6), and consequently accelerating the construction of C(sp3)?N bond. The reaction proceeded efficiently with a wide array of hydrocarbons and P(O)?NH compounds, and the rate acceleration induced by the acetic acid coproduct have been repeatedly proven. Furthermore, the efficiency of small-scale reaction could be retained upon gram-scale synthesis in a continuous manner. (Figure presented.).
Lei, Jian,Yang, Yincai,Peng, Lingteng,Wu, Lesong,Peng, Ping,Qiu, Renhua,Chen, Yi,Au, Chak-Tong,Yin, Shuang-Feng
supporting information
p. 1689 - 1696
(2019/03/07)

Cobaloxime Catalysis: selective synthesis of alkenylphosphine oxides under visible light
Direct activation of H-phosphine oxide to react with an unsaturated carbon-carbon bond is a straightforward approach for accessing alkenylphosphine oxides, which shows significant applications in both synthetic and material fields. However, expensive metals and strong oxidants are typically required to realize the transformation. Here, we demonstrate the utility of earth-abundant cobaloxime to convert H-phosphine oxide into its reactive radical species under visible light irradiation. The radical species thus generated can be utilized to functionalize alkenes and alkynes without any external photosensitizer and oxidant. The coupling with terminal alkene generates E-alkenylphosphine oxide with excellent chemo- A nd stereoselectivity. The reaction with terminal alkyne yields linear E-alkenylphosphine oxide via neutral radical addition, while addition with internal ones generates cyclic benzophosphine oxides and hydrogen. Mechanistic studies on radical trapping experiments, electron spin resonance studies, and spectroscopic measurements confirm the formation of phosphinoyl radical and cobalt intermediates that are from capturing the electron and proton eliminated from H-phosphine oxide. The highlight of our mechanistic investigation is the dual role played by cobaloxime, viz., both as the visible light absorber to activate the P(O)-H bond as well as a hydrogen transfer agent to influence the reaction pathway. This synergetic feature of the cobaloxime catalyst preforming multiple functions under ambient condition provides a convergent synthetic approach to vinylphosphine oxides directly from H-phosphine oxides and alkenes (or alkynes).
Liu, Wen-Qiang,Lei, Tao,Zhou, Shuai,Yang, Xiu-Long,Li, Jian,Chen, Bin,Sivaguru, Jayaraman,Tung, Chen-Ho,Wu, Li-Zhu
supporting information
p. 13941 - 13947
(2019/09/30)

Cobaloxime Catalysis: Selective Synthesis of Alkenylphosphine Oxides under Visible Light
Direct activation of H-phosphine oxide to react with an unsaturated carbon-carbon bond is a straightforward approach for accessing alkenylphosphine oxides, which shows significant applications in both synthetic and material fields. However, expensive metals and strong oxidants are typically required to realize the transformation. Here, we demonstrate the utility of earth-abundant cobaloxime to convert H-phosphine oxide into its reactive radical species under visible light irradiation. The radical species thus generated can be utilized to functionalize alkenes and alkynes without any external photosensitizer and oxidant. The coupling with terminal alkene generates E-alkenylphosphine oxide with excellent chemo- and stereoselectivity. The reaction with terminal alkyne yields linear E-alkenylphosphine oxide via neutral radical addition, while addition with internal ones generates cyclic benzophosphine oxides and hydrogen. Mechanistic studies on radical trapping experiments, electron spin resonance studies, and spectroscopic measurements confirm the formation of phosphinoyl radical and cobalt intermediates that are from capturing the electron and proton eliminated from H-phosphine oxide. The highlight of our mechanistic investigation is the dual role played by cobaloxime, viz., both as the visible light absorber to activate the P(O)-H bond as well as a hydrogen transfer agent to influence the reaction pathway. This synergetic feature of the cobaloxime catalyst preforming multiple functions under ambient condition provides a convergent synthetic approach to vinylphosphine oxides directly from H-phosphine oxides and alkenes (or alkynes).
Liu, Wen-Qiang,Lei, Tao,Zhou, Shuai,Yang, Xiu-Long,Li, Jian,Chen, Bin,Sivaguru, Jayaraman,Tung, Chen-Ho,Wu, Li-Zhu
supporting information
p. 13941 - 13947
(2019/09/30)

Rhodium catalyzed C-C bond cleavage/coupling of 2-(azetidin-3-ylidene)acetates and analogs
The C-C bond cleavage/coupling of 2-(azetidin-3-ylidene)acetates with aryl boronic acids catalyzed by a rhodium complex was studied with a "conjugate addition/β-C cleavage/protonation" strategy.
Yang, Xuan,Kong, Wei-Yu,Gao, Jia-Ni,Cheng, Li,Li, Nan-Nan,Li, Meng,Li, Hui-Ting,Fan, Jun,Gao, Jin-Ming,Ouyang, Qin,Xie, Jian-Bo
supporting information
p. 12707 - 12710
(2019/10/28)

Silver-promoted cascade radical cyclization of γ,δ-unsaturated oxime esters with P(O)H compounds: synthesis of phosphorylated pyrrolines
A cascade radical cyclization was realized for the first silver-promoted imino-phosphorylation of γ,δ-unsaturated oxime esters, which provided a step-economical and redox-neutral route to access a variety of phosphorylated pyrrolines in good to excellent yields. Moreover, a new bulky trivalent phosphine ligand with a pyrroline motif was obtained through a deoxidation process.
Chen, Chen,Bao, Yinwei,Zhao, Jinghui,Zhu, Bolin
supporting information
p. 14697 - 14700
(2019/12/11)

NHC-Catalyzed Synthesis of Benzazole-Phosphine Ligands under an Air Atmosphere
An efficient strategy for the synthesis of benzazole-phosphine ligand precursors via N -heterocyclic carbene catalyzed aerobic oxidative cyclization reaction has been performed. The reaction displays broad functional group tolerance and high atom economy,
Ren, Wei,Yang, Shang-Dong,Zuo, Qian-Ming
p. 1719 - 1724
(2019/08/28)

Preparation of O-Protected Cyanohydrins by Aerobic Oxidation of α-Substituted Malononitriles in the Presence of Diarylphosphine Oxides
A mild, reagent-cyanide-free, and efficient synthesis of O-phosphinoyl-protected cyanohydrins from readily available α-substituted malononitriles was realized using diarylphosphine oxides in the presence of O2. Mechanistic studies indicated that in addition to the initial aerobic oxidation of the malononitrile derivative notable features of this process include the formation of a tetrahedral intermediate and a subsequent intramolecular rearrangement. The phosphinoyl-protecting group can be removed by alcoholysis or by reduction with DIBAL-H.
Zhang, Dapeng,Lian, Mingming,Liu, Jia,Tang, Shukun,Liu, Guangzhi,Ma, Cunfei,Meng, Qingwei,Peng, Haisheng,Zhu, Daling
supporting information
p. 2597 - 2601
(2019/04/17)

Siladifluoromethylation and Deoxo-trifluoromethylation of PV-H Compounds with TMSCF3: Route to PV-CF2- Transfer Reagents and P-CF3 Compounds
A method for siladifluoromethylation of dialkyl phosphonates and secondary phosphine oxides with TMSCF3 to produce nucleophilic PV-CF2- transfer reagents is disclosed, with multigram scale reactions included. Condition-dependent divergent reactivity under the established conditions is demonstrated by the formation of trifluoromethylphosphines. Both one-pot transformations are operationally simple and employ inexpensive materials. Mechanistic investigations suggest the divergent reactivity originates from a common intermediate, with Li+ concentration directing the chemoselectivity.
Krishnamurti, Vinayak,Barrett, Colby,Prakash, G. K. Surya
supporting information
p. 1526 - 1529
(2019/03/07)

Electrochemical Dehydrogenative Phosphorylation of Alcohols for the Synthesis of Organophosphinates
An eco-friendly and efficient method for the synthesis of organophosphinates via an electrochemical cross-dehydrogenative-coupling reaction between alcohols and secondary phosphine oxides has been developed. This electrochemical reaction was conducted at
Deng, Lingling,Wang, Yang,Mei, Haibo,Pan, Yi,Han, Jianlin
p. 949 - 956
(2019/01/14)

Palladium-Catalyzed C-P Cross-Coupling between (Het)aryl Halides and Secondary Phosphine Oxides
An efficient procedure for C-P bond formation via the palladium-catalyzed [Pd(OAc) 2 /dppf/Cs 2 CO 3 ] reaction between dichloroheterocycles and secondary phosphine oxides was developed. The steric and electronic properties of substituents were varied to establish the scope and limitations of the method developed. By applying these conditions, a variety of new heterocyclic compounds bearing two tertiary phosphine oxides were successfully synthesized in moderate to excellent yields. After adjustments to the reaction conditions [Pd(OAc) 2 /dippf/ t -BuOK], cross-coupling of secondary phosphine oxides with bulky (secondary or tertiary alkyl) substituents on the phosphorus atom was achieved. Extension of the methodology to monohalohetarenes and monohaloarenes was successfully carried out; once again, the steric and electronic properties of the halides were varied widely. The desired reaction occurred in all cases studied, giving high to excellent yields of product regardless of the nature and positions of substituents.
Zakirova, Gladis G.,Mladentsev, Dmitrii Yu.,Borisova, Nataliya E.
p. 2379 - 2386
(2019/05/24)

Chelation-assisted C-N cross-coupling of phosphinamides and aryl boronic acids with copper powder at room temperature
A protocol for the chelation-assisted C-N cross-coupling of phosphinamides and aryl boronic acids with copper powder under an oxygen atmosphere is reported. This reaction proceeds efficiently to afford fully substituted unsymmetrical N-arylation phosphinamides at room temperature in excellent yields. Diverse unstable functional groups on the benzene ring of aryl boronic acids such as vinyl, formyl, acetyl, sulfonyl, acetylamino, cyano, nitro, and trifluoromethyl can be accommodated.
Peng, Yao,Lei, Jian,Qiu, Renhua,Peng, Lingteng,Au, Chak-Tong,Yin, Shuang-Feng
supporting information
p. 4065 - 4070
(2018/06/12)

Copper-catalyzed C–P cross-coupling of secondary phosphines with (hetero)aromatic bromide
A novel and convenient approach to the synthesis of various tertiary phosphines via a copper-catalyzed cross-coupling of (hetero)aromatic bromide with secondary phosphines has been developed. The reaction employs cheap copper as the catalyst, 2,6-bis(N-methylaminomethyl)pyridine (L4) as a perfect ligand and KOtBu as a base; all reactions are carried out under argon atmosphere. A variety of sterically hindered and/or functionalized substrates were found to react under these reaction conditions to provide products in good to excellent yields. Moreover, ten new tertiary phosphines were first reported in this process.
Li, Chun-Jing,Lü, Jing,Zhang, Zhi-Xun,Zhou, Kun,Li, Yan,Qi, Guang-Hui
p. 4547 - 4562
(2018/04/20)

Asymmetric Covalent Triazine Framework for Enhanced Visible-Light Photoredox Catalysis via Energy Transfer Cascade
Complex multiple-component semiconductor photocatalysts can be constructed that display enhanced catalytic efficiency via multiple charge and energy transfer, mimicking photosystems in nature. In contrast, the efficiency of single-component semiconductor photocatalysts is usually limited due to the fast recombination of the photogenerated excitons. Here, we report the design of an asymmetric covalent triazine framework as an efficient organic single-component semiconductor photocatalyst. Four different molecular donor–acceptor domains are obtained within the network, leading to enhanced photogenerated charge separation via an intramolecular energy transfer cascade. The photocatalytic efficiency of the asymmetric covalent triazine framework is superior to that of its symmetric counterparts; this was demonstrated by the visible-light-driven formation of benzophosphole oxides from diphenylphosphine oxide and diphenylacetylene.
Huang, Wei,Byun, Jeehye,R?rich, Irina,Ramanan, Charusheela,Blom, Paul W. M.,Lu, Hao,Wang, Di,Caire da Silva, Lucas,Li, Run,Wang, Lei,Landfester, Katharina,Zhang, Kai A. I.
supporting information
p. 8316 - 8320
(2018/06/29)

Tailored Cobalt-Catalysts for Reductive Alkylation of Anilines with Carboxylic Acids under Mild Conditions
The first cobalt-catalyzed hydrogenative N-methylation and alkylation of amines with readily available carboxylic acid feedstocks as alkylating agents and H2 as ideal reductant is described. Combination of tailor-made triphos ligands with cobalt(II) tetrafluoroborate significantly improved the efficiency, thus promoting the reaction under milder conditions. This novel protocol allows for a broad substrate scope with good functional group tolerance, even in the presence of reducible alkenes, esters, and amides.
Liu, Weiping,Sahoo, Basudev,Spannenberg, Anke,Junge, Kathrin,Beller, Matthias
supporting information
p. 11673 - 11677
(2018/09/10)

Dearylation of arylphosphine oxides using a sodium hydride-iodide composite
A new protocol for the dearylation of arylphosphine oxides was developed using sodium hydride (NaH) in the presence of lithium iodide (LiI). The transient sodium phosphinite could be functionalized with a range of electrophiles in a one-pot fashion.
Tejo, Ciputra,Pang, Jia Hao,Ong, Derek Yiren,Oi, Miku,Uchiyama, Masanobu,Takita, Ryo,Chiba, Shunsuke
supporting information
p. 1782 - 1785
(2018/02/21)

Rapid Metal-Free Formation of Free Phosphines from Phosphine Oxides
A rapid method for the reduction of secondary phosphine oxides under mild conditions has been developed, allowing simple isolation of the corresponding free phosphines. The methodology involves the use of pinacol borane (HBpin) to effect the reduction while circumventing the formation of a phosphine borane adduct, as is usually the case with various other commonly used borane reducing agents such as borane tetrahydrofuran complex (BH3?THF) and borane dimethyl sulfide complex (BH3?SMe2). In addition, this methodology requires only a small excess of reducing agent and therefore compares favourably not just with other borane reductants that do not require a metal co-catalyst, but also with silane and aluminium based reagents. (Figure presented.).
Provis-Evans, Cei B.,Emanuelsson, Emma A. C.,Webster, Ruth L.
supporting information
p. 3999 - 4004
(2018/09/21)

Selective P?C(sp3) Bond Cleavage and Radical Alkynylation of α-Phosphorus Alcohols by Photoredox Catalysis
Herein the first P?C(sp3) bond cleavage and radical alkynylation of α-phosphorus alcohols to construct phosphonoalkynes is reported. The phosphorus radical is generated upon P?C bond cleavage reaction via the alkoxyl radical through photoredox catalysis with cyclic iodine(III) reagents. Various arylphosphinoyl-, alkylphosphinoyl-, phosphonate-, and phosphonic amide alcohols serve as radical phosphorus precursors to construct phosphonoalkynes for the first time.
Jia, Kunfang,Li, Junzhao,Chen, Yiyun
supporting information
p. 3174 - 3177
(2018/02/09)

Outer-Sphere Reactivity Shift of Secondary Phosphine Oxide-Based Nickel Complexes: From Ethylene Hydrophosphinylation to Oligomerization
A new dimension for secondary phosphine oxide (SPOs) ligands is described in this article. Demonstrated on original π-allylic nickel structures, these self-assembled complexes trigger catalytic hydrophosphinylation reactions. Addition of a Lewis acid B(C6F5)3 switches the reactivity towards migratory insertion and thus ethylene oligomerization through an unprecedented outer-sphere interaction with the coordinated SPO ligand. NMR experiments and X-ray analyses allowed for the observation of the formation of zwitterionic active species as well as their degradation pathway.
Lhermet, Rudy,Moser, Emile,Jeanneau, Erwann,Olivier-Bourbigou, Hélène,Breuil, Pierre-Alain R.
supporting information
p. 7433 - 7437
(2017/06/06)

Rhodium(III)-Catalyzed Enantiotopic C?H Activation Enables Access to P-Chiral Cyclic Phosphinamides
Compounds with stereogenic phosphorus atoms are frequently used as ligands for transition-metal as well as organocatalysts. A direct catalytic enantioselective method for the synthesis of P-chiral compounds from easily accessible diaryl phosphinamides is presented. The use of rhodium(III) complexes equipped with a suitable atropochiral cyclopentadienyl ligand is shown to enable an enantiodetermining C?H activation step. Upon trapping with alkynes, a broad variety of cyclic phosphinamides with a stereogenic phosphorus(V) atom are formed in high yields and enantioselectivities. Moreover, these can be reduced enantiospecifically to P-chiral phosphorus(III) compounds.
Sun, Yang,Cramer, Nicolai
supporting information
p. 364 - 367
(2016/12/30)

Preparation of organophosphorus compounds from P-H compounds using o-(trimethylsilyl)aryl triflates as aryne precursors
An efficient method was developed for the synthesis of a variety of arylphosphorus compounds from P-H compounds using o-(trimethylsilyl)aryl triflates as aryne precursors. The reaction provides a practical preparation of various arylphosphorus compounds via aryne intermediates utilizing diarylphosphine oxides and dialkyl phosphites as the nucleophiles.
Yang, Guoqiang,Shen, Chaoren,Quan, Mao,Zhang, Wanbin
supporting information
p. 333 - 337
(2015/12/30)

Convenient synthesis of allenylphosphoryl compounds: Via Cu-catalysed couplings of P(O)H compounds with propargyl acetates
A novel Cu-catalysed substitution reaction of propargyl acetates with P(O)H compounds is developed to afford allenylphosphoryl compounds via C-P bond coupling in high yields under mild conditions. A plausible mechanism involving the nucleophilic interception of the Cu-allenylidene intermediates is proposed.
Shen, Ruwei,Luo, Bing,Yang, Jianlin,Zhang, Lixiong,Han, Li-Biao
supporting information
p. 6451 - 6454
(2016/05/24)

Photoinduced reductive perfluoroalkylation of phosphine oxides: synthesis of P-perfluoroalkylated phosphines using TMDPO and perfluoroalkyl iodides
A photoinduced reaction between TMDPO (diphenyl(2,4,6-trimethylbenzoyl)-phosphine oxide) and perfluoroalkyl iodides successfully affords P-(perfluoroalkyl)diphenylphosphines as promising ligands for recyclable catalysts. Interestingly, the perfluoroalkylation reaction involves the reduction of phosphorus(v) compounds to phosphorus(iii) species. The advantages of the present reaction include the use of an air-stable phosphorus source and good yields of P-perfluoroalkylphosphines in short reaction times.
Sato, Yuki,Kawaguchi, Shin-Ichi,Ogawa, Akiya
supporting information
p. 10385 - 10388
(2015/06/25)

Selective dehydrocoupling of phosphines by lithium chloride carbenoids
The development of a simple, transition-metal-free approach for the formation of phosphorus-phosphorus bonds through dehydrocoupling of phosphines is presented. The reaction is mediated by electronically stabilized lithium chloride carbenoids and affords a variety of different diphosphines under mild reaction conditions. The developed protocol is simple and highly efficient and allows the isolation of novel functionalized diphosphines in high yields.
Molitor, Sebastian,Becker, Julia,Gessner, Viktoria H.
supporting information
p. 15517 - 15520
(2014/12/12)

Synthesis of gem-difluorocyclopropa(e)nes and O-, S-, N-, and P-difluoromethylated compounds with TMSCF2Br
Two-in-one: Me3SiCF2Br is an efficient difluorocarbene source and is compatible with both neutral and aqueous basic conditions. Bromide-ion-initiated [2+1] cycloaddition with alkenes/alkynes and hydroxide ion promoted α-addition with (thio)phenols, (thio)alcohols, sulfinates, heterocyclic amines, and H-phosphine oxides give the corresponding gem-difluorinated compounds with broad functional-group tolerance. Copyright
Li, Lingchun,Wang, Fei,Ni, Chuanfa,Hu, Jinbo
supporting information
p. 12390 - 12394
(2013/12/04)

Synthesis of new BINAP-based aminophosphines and their 31P-NMR spectroscopy
BINAP aminophosphines are prevalent N,P-bidentate, chiral ligands for asymmetric catalysis. While modification via the BINAP-nitrogen linkage is well explored and has provided a diverse body of derivatives, modification of the other substituents of the phosphorous center is another avenue in generating new congeners of this important class of chiral ligands. Herein reported are new BINAP aryl aminophosphines with electron rich or deficient substituents on the aryl rings. This scalable synthesis converted readily available starting material, (S)-BINOL, to a key intermediate (S)-NOBIN, from which the final chiral aminophosphines were prepared via a palladium-catalyzed, phosphonylation reaction. The aryl substituents are able to modify the electronic properties of the phosphorous center as indicated by the range of 31P-NMR shifts of these new ligands. A computational analysis was performed to linearly quantitate contributions to the 31P-NMR shifts from both resonance and field effects of the substituents. This correlation may be useful for designing and preparing other related aminophosphines with varying ligand properties.
Anstiss, Christopher,Karuso, Peter,Richardson, Mark,Liu, Fei
p. 2788 - 2802
(2013/05/09)

Process research on the asymmetric hydrogenation of a benzophenone for developing the manufacturing process of the squalene synthase inhibitor TAK-475
A practical synthetic method for the synthesis of the chiral benzhydrol 8, which is the key intermediate of the squalene synthase inhibitor TAK-475 (1), has been developed. The method, via asymmetric hydrogenation of the benzophenone 7, employed Noyori's ruthenium precatalyst of the type [RuCl 2(diphosphine)(diamine). We focused on tuning of the chiral diphosphine, and have discovered a novel ligand, DADMP-BINAP (18c), for the catalyst that has allowed reduction of the operating pressure in the asymmetric hydrogenation. The precatalyst containing 18c performed effectively at low hydrogen pressure (1 MPa) with sufficient enantioselectivity, and the result enabled us to successfully obtain enantiomerically pure 8 on a multikilogram scale.
Goto, Mitsutaka,Konishi, Takahiro,Kawaguchi, Shinji,Yamada, Masatoshi,Nagata, Toshiaki,Yamano, Mitsuhisa
scheme or table
p. 1178 - 1184
(2011/12/16)

Catalytic asymmetric hydrogenation of α-ketoesters and quinoline using electronically enriched BINAP
Electronically enriched chiral BINAP derivatives were synthesized incorporating electron-donating substituents at the para-phenyl position and evaluated for the Ru-catalyzed homogeneous asymmetric hydrogenation of α-ketoesters with up to 92% ee. These diphophosphines were also excellent ligands for the iridium-catalyzed asymmetric hydrogenation of quinolines.
Jahjah, Mohamad,Alame, Mohamad,Pellet-Rostaing, Stephane,Lemaire, Marc
p. 2305 - 2312
(2008/03/12)

PROCESS FOR PRODUCTION OF PHOSPHINE-BORANE COMPLEXES
A process for the production of phosphine-borane complexes represented by the general formula: or salts thereof: [wherein R1, R2 and R3 are each independently a hydrogen atom, a halogen atom, an optionally substituted alky
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(2008/06/13)

A superior method for the reduction of secondary phosphine oxides
(Chemical Equation Presented) Diisobutylaluminum hydride (DIBAL-H) and triisobutylaluminum have been found to be outstanding reductants for secondary phosphine oxides (SPOs). All classes of SPOs can be readily reduced, including diaryl, arylalkyl, and dialkyl members. Many SPOs can now be reduced at cryogenic temperatures, and conditions for preservation of reducible functional groups have been found. Even the most electron-rich and sterically hindered phosphine oxides can be reduced in a few hours at 50-70°C. This new reduction has distinct advantages over existing technologies.
Busacca, Carl A.,Lorenz, Jon C.,Grinberg, Nelu,Haddad, Nizar,Hrapchak, Matt,Latli, Bachir,Lee, Heewon,Sabila, Paul,Saha, Anjan,Sarvestani, Max,Shen, Sherry,Varsolona, Richard,Wei, Xudong,Senanayake, Chris H.
p. 4277 - 4280
(2007/10/03)

Electronic and steric effects of ligands as control elements for rhodium-catalyzed asymmetric hydrogenation
Chiral diphosphine ligands analogous to bdpp have been synthesized and tested in order to study the effect of the electronic nature of the ligands in Rh-catalyzed asymmetric hydrogenation of some prochiral olefins. The results are compared with those obtained with the analogous unsubstituted ligand (bdpp). The rhodium-catalyzed asymmetric hydrogenation of olefins was influenced by ligand-based electronic effects, as well as substrate based ones. Excellent ee's (up to 98.3%) have been obtained in the rhodium-catalyzed hydrogenation of (Z)-α-acetamidocinnamic acids and esters.
Herseczki, Zsanett,Gergely, Ildiko,Hegedues, Csaba,Szoellosy, Aron,Bakos, Jozsef
p. 1673 - 1676
(2007/10/03)

PROCESS FOR PREPARATION OF DIPHOSPHINE COMPOUNDS AND INTERMEDIATES FOR THE PROCESS
A production method of a_compound represented by the formula wherein R1a, R1b, R1c, R1d, R1e, R1f, R2a, R2b, R2c R2d, R2e and R2f are the same or different and each is a hydrogen atom and the like, and R3, R4, R5, R6, R7, R8, R9 and R10 are the same or different and each is a hydrogen atom and the like, or a salt thereof, which comprises reacting a compound represented by the formula wherein X is a leaving group and other symbols are as defined above, or a salt thereof, with a phosphine-borane complex represented by the formula wherein the symbols are as defined above, or a salt thereof, in a solvent in the presence of an amine and a nickel catalyst, is provided.
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(2008/06/13)