- Enantioselective Pd0-Catalyzed C(sp2)–H Arylation for the Synthesis of Chiral Warped Molecules
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C?H activation-based ring-forming methods are a powerful approach for the construction of complex molecular architectures, especially those containing a congested stereocenter. Therefore, this strategy seems perfectly suited to address the synthesis of ch
- Savary, David,Baudoin, Olivier
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supporting information
p. 5136 - 5140
(2021/01/21)
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- Highly Enantioselective Synthesis of Phosphorus-Containing ?-Benzosultams by Bifunctional Phosphonium Salt-Promoted Hydrophosphonylation
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?-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
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supporting information
p. 11285 - 11290
(2021/07/02)
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- Twofold C?H Activation-Based Enantio- and Diastereoselective C?H Arylation Using Diarylacetylenes as Rare Arylating Reagents
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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
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supporting information
p. 20424 - 20429
(2021/08/09)
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- Visible-light-driven metal-free aerobic synthesis of highly diastereoselective phosphinoylpyrroloindoles
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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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supporting information
p. 1354 - 1358
(2020/03/03)
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- Copper mediated C(sp2)-H amination and hydroxylation of phosphinamides
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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
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supporting information
p. 1444 - 1447
(2020/02/11)
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- 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
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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
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supporting information
p. 1689 - 1696
(2019/03/07)
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- Cobaloxime Catalysis: selective synthesis of alkenylphosphine oxides under visible light
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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
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supporting information
p. 13941 - 13947
(2019/09/30)
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- Cobaloxime Catalysis: Selective Synthesis of Alkenylphosphine Oxides under Visible Light
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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
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supporting information
p. 13941 - 13947
(2019/09/30)
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- Preparation of O-Protected Cyanohydrins by Aerobic Oxidation of α-Substituted Malononitriles in the Presence of Diarylphosphine Oxides
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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
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supporting information
p. 2597 - 2601
(2019/04/17)
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- Electrochemical Dehydrogenative Phosphorylation of Alcohols for the Synthesis of Organophosphinates
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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
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p. 949 - 956
(2019/01/14)
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- Highly chemo- and regioselective C-P cross-coupling reaction of quinone imine ketals with Ar2P(O)H to construct: Ortho -amino triarylphosphine derivatives
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A highly chemo- and regioselective approach for the construction of ortho-amino triarylphosphine oxides has been achieved through a C-P cross-coupling reaction involving quinone imine ketals (QIKs) with Ar2P(O)H and catalyzed via a Lewis base. This alternative protocol provided a wide substrate scope with excellent yields (82-95%), and a variety of ortho-amino triarylphosphines were obtained with high yields (87-95%) via further reductive reaction. Furthermore, this reaction could be scaled-up and several synthetic transformations were accomplished for the construction of functionalized organophosphorus.
- Liu, Teng,Li, Yongqin,Cheng, Feixiang,Shen, Xianfu,Liu, Jianjun,Lin, Jun
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supporting information
p. 3536 - 3541
(2019/07/10)
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- Chelation-assisted C-N cross-coupling of phosphinamides and aryl boronic acids with copper powder at room temperature
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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
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supporting information
p. 4065 - 4070
(2018/06/12)
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- Selective P?C(sp3) Bond Cleavage and Radical Alkynylation of α-Phosphorus Alcohols by Photoredox Catalysis
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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
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supporting information
p. 3174 - 3177
(2018/02/09)
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- Rhodium(III)-Catalyzed Enantiotopic C?H Activation Enables Access to P-Chiral Cyclic Phosphinamides
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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
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supporting information
p. 364 - 367
(2016/12/30)
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- Dioxygen-induced oxidative activation of a P-H bond: Radical oxyphosphorylation of alkenes and alkynes toward β-oxy phosphonates
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The dioxygen-induced radical oxyphosphorylation of alkenes and alkynes is presented, wherein a P-H bond was activated by molecular oxygen. Various β-oxy phosphonates could be facilely synthesized without the assistance of any transition metals or extra or
- Peng, Pan,Lu, Qingquan,Peng, Long,Liu, Chao,Wang, Guangyu,Lei, Aiwen
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supporting information
p. 12338 - 12341
(2016/10/22)
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- Pd(II)-catalyzed enantioselective synthesis of P-stereogenic phosphinamides via desymmetric C-H arylation
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We present the enantioselective synthesis of P-stereogenic phosphinamides through Pd-catalyzed desymmetric ortho C-H arylation of diarylphosphinamides with boronic esters. The method represents the first example of the synthesis of P-stereogenic phosphorus compounds via the desymmetric C-H functionalization strategy. The reaction proceeded efficiently with a wide array of reaction partners to afford the P-stereogenic phosphinamides in up to 74% yield and 98% ee. The efficiency was further demonstrated by gram scale syntheses. Moreover, the flexible conversion of the P-stereogenic phosphinamides into various types of P-stereogenic phosphorus derivatives was also elaborated. Thus, the protocol provides a novel tool for the efficient and versatile synthesis of P-stereogenic compounds.
- Du, Zhi-Jun,Guan, Jing,Wu, Guo-Jie,Xu, Peng,Gao, Lian-Xun,Han, Fu-She
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supporting information
p. 632 - 635
(2015/01/30)
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- PROCESS FOR PREPARATION OF DIPHOSPHINE COMPOUNDS AND INTERMEDIATES FOR THE PROCESS
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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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