Alkynylphosphonation of Unactivated Olefins via Radical-Triggered 1, 2-Alkynyl Migration

Citation: Zhang Ping, Shi Haonan, Zhang Tianshu, Cai Peijun, Jiang Bo, Tu Shujiang. Alkynylphosphonation of Unactivated Olefins via Radical-Triggered 1, 2-Alkynyl Migration[J]. Chinese Journal of Organic Chemistry, 2020, 40(2): 423-431. doi: 10.6023/cjoc201909007 shu

利用自由基引发的1, 2-炔基迁移实现非活性烯烃的炔膦酰化

张萍 ^a,c, ,
石浩楠 ^b, ,
张天舒 ^a, ,
蔡佩君 ^{a,
,} ,
姜波 ^b, ,
屠树江 ^{b,
,}

a.
中国矿业大学化工学院江苏徐州 221116
b.
江苏师范大学化学与材料科学学院江苏徐州 221116
c.
江苏省徐州医药高等职业学校江苏徐州 221116

通讯作者: 蔡佩君, pjcai@cumt.edu.cn
屠树江, laotu@jsnu.edu.cn

基金项目:
中央高校基本科研专项资金基金 JH180263

中央高校基本科研专项资金基金（No.JH180263）资助项目

摘要: 研究了1，4-烯炔衍生物与二芳基膦氧化物在银介导下发生的炔酰化反应.该反应利用自由基引发的1，2-炔基迁移策略合成了一系列γ-酮膦氧化物，产率适中.该反应机理可能涉及膦中心自由基与乙烯基的加成、3-exo-dig环化和1，2-炔基迁移等连续的过程，一步形成了C-P、C-C键等化学键，实现了非活性烯烃的双官能化.

关键词:

English

Alkynylphosphonation of Unactivated Olefins via Radical-Triggered 1, 2-Alkynyl Migration

a.
School of Chemical Engineering & Technology, China University of Mining and Technology, Xuzhou, Jiangsu 221116
b.
School of Chemistry & Materials Science, Jiangsu Normal University, Xuzhou, Jiangsu 221116
c.
Jiangsu Provincial Xuzhou Pharmaceutical Vocational College, Xuzhou, Jiangsu 221116

Corresponding author: Cai Peijun, pjcai@cumt.edu.cn Tu Shujiang, laotu@jsnu.edu.cn

Received Date: 04 September 2019
Revised Date: 16 October 2019
Available Online: 25 February 2020
Fund Project:
the Fundamental Research Funds for the Central Universities JH180263

Project supported by the Fundamental Research Funds for the Central Universities (No. JH180263)

Abstract: A silver-mediated alkynylphosphonation of 1, 4-enynes with diarylphosphine oxides has been developed, by which a wide range of γ-ketophosphine oxides with moderate to good yields were synthesized through radical 1, 2-alkynyl migration. The transformation proceeded with sequential P-centered radical addition to vinyl unit, 3-exo-dig cyclization and 1, 2-alkynyl migration, resulting in the bond-forming events including C-P and C-C bonds to realize difunctionalization of unactivated olefins.

Key words:

1. Introduction

As highly important and valuable feedstocks, alkenes have been widely utilized for myriad challenging and intriguing transformations in synthetic science due to their unique reactivity profile.^[1] Specifically, radical-induced direct 1, 2-difunctionalization of alkenes has emerged as a significant synthetic tool for the collection of highly functionalized molecules by incorporating two functional groups across the C＝C π system.^[2] A extensive survey of literature reports revealed that the vast majority of well-developed methods generally depend on activated alkenes, due to its nascent alkyl radical needs to be stabilized by adjacent functional groups (e.g. aryl, carbonyl, heteroatom) via p-π conjugate effect (Scheme 1, path i).^[3] However, radical induced difunctionalization of unactivated alkenes remains elusive. On the other hand, the radical functionality migration enables to reconstruct the molecular structures and assemble significant compounds which are not available through other methods.^[4] Such reaction category provides a new synthetic protocol for radical difunctionalization of unactivated alkenes.^[5] Numerous state-of-the-art works for intramolecular functionality migration strategies, such as arylation, ^[6] cyanation, ^[7] imidization, ^[8] formylation, ^[9] heteroarylation^[10] and alkenylation^[11] have been reported (Scheme 1, pathway iii). Very recently, Zhu group^[12] pioneered the intramolecular distal alkynyl migration for alkynylation of unactivated olefins (Scheme 1, path ii). However, these cases were restricted to distal 1, 4- or 1, 5-alkynyl migration. To achieve radical 1, 2-alkynyl migration, an isopropenyl group was adopted to replace the vinyl moiety in the enyne substrates to prepare a class of new 1, 4-enynes, and it found that these substrates underwent radical 3-exo-dig cyclization and C—C σ bond cleavage to complete their 1, 2-alkynyl migration triggered by C-centered or H radical species (Scheme 1, path iii).^[13] To further investigate the generality of radical 1, 2-alkynyl migration of 1, 4-enynes and expand the family of α-alkynyl ketones, we attempted to utilize diarylphosphine oxides as P-centered radical precursors to trigger 1, 2-alkynyl migration of 1, 4-enynes to construct γ-ketophosphine oxides due to such compounds have been found to exhibit wide-spectrum biological activities and unique properties.^[14] Herein, we describe a silver- mediated alkynylphosphonation of 1, 4-enynes with diaryl- phosphine oxides, in which a series of α-alkynyl γ-keto- phosphine oxides were obtained through a sequential P- centered radical addition, 3-exo-dig cyclization and 1, 2- alkynyl migration cascade (Scheme 1, path iv).^[15]

Scheme 1

Scheme 1. Profiles of radical-mediated functionalization of alkenes

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2. Results and discussion

Our initial investigations focused on identifying the optimized conditions by selecting the preformed 1, 4-enyne 1a and diphenylphosphine oxide 2a as the model substrates. The reaction of 1a with 2a was conducted in the presence of AgNO₃ (2.0 equiv.) in a mixed solvent of CH₃CN and H₂O at 80 ℃, and the expected migration product 3a was generated, albeit with a low 17% yield (Table 1, Entry 1). Subsequently, several silver salts such as AgOAc, Ag₂CO₃ and Ag₂O were screened, indicating that AgOAc substantially suppressed the formation of 3a (Entry 2) while the latter two could accelerate this radical transformation (Entries 3, 4) and the last one showed the best oxidation ability, offering in 39% yield (Entr y 4). The following screening of other aprotic solvents, such as 1, 2-dichloroethane (DCE), methanol, N, N-dimethylforma- mide (DMF) and 1, 4-dioxane revealed that all these solvents have no positive effect on the yield of 3a as compared with CH₃CN (Entries 5~8 vs Entry 4). Adjusting the amount of Ag₂O to 1.0 equiv. was not beneficial for this transformation with observation of unconsumed starting materials (Entry 9). An increase of the amount of Ag₂O to 3.0 equiv. led to a higher yield of product 3a (53%, Entry 10). The yield of 3a levelled off when the loading of Ag₂O was further increased (Entry 11). Next, we attempted to change reaction temperatures to assess the effect on the efficiency of the reaction. After careful investigations, the reaction temperature was found to have remarkable influence on this radical transformation (Entries 12, 13). Elevating reaction temperature from 80 ℃ to 100 ℃ facilitated the reaction process, and an almost full consumption of the starting material was observed at 100 ℃, giving 64% yield. Further raising the temperature to 120 ℃ did not improve the conversion of 1a into 3a (Entry 14). Without H₂O, the lower conversion was observed (Entry 15).

Table 1

Table 1. Optimization of reaction conditions^a

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Entry	Ag salt (equiv.)	Solvent	t/℃	Yield^b/%
1	AgNO₃ (2.0)	CH₃CN/H₂O	80	17
2	AgOAc (2.0)	CH₃CN/H₂O	80	6
3	Ag₂CO₃ (2.0)	CH₃CN/H₂O	80	26
4	Ag₂O (2.0)	CH₃CN/H₂O	80	39
5	Ag₂O (2.0)	DCE/H₂O	80	Trace
6	Ag₂O (2.0)	MeOH/H₂O	80	20
7	Ag₂O (2.0)	DMF/H₂O	80	20
8	Ag₂O (2.0)	1, 4-Dioxane/H₂O	80	17
9	Ag₂O (1.0)	CH₃CN/H₂O	80	18
10	Ag₂O (3.0)	CH₃CN/H₂O	80	53
11	Ag₂O (4.0)	CH₃CN/H₂O	80	53
12	Ag₂O (3.0)	CH₃CN/H₂O	90	57
13	Ag₂O (3.0)	CH₃CN/H₂O	100	64
14	Ag₂O (3.0)	CH₃CN/H₂O	110	63
15	Ag₂O (3.0)	CH₃CN	100	45
^a Reaction conditions: 1a (0.2 mmol), 2a (0.2 mmol), silver salt, organic solvent (3.0 mL), H₂O (0.5 mL). ^b Isolated yield based on 1a.

With the optimized reaction conditions in hand, we then set out to study the generality of the migration reaction by examining 1, 4-enyne and diarylphosphine oxide components (Table 2). 1, 4-Enynes 1 with diverse substituents on the arylalkynyl moiety (R) were first investigated in combination with diphenylphosphine oxide (2a) under the standard conditions. Both electron-poor and electron-rich groups at different positions were accommodated well, accessing the corresponding products 3b~3n in 40%~68% yields. The different substituents including fluoro, chloro), bromo, methyl, ethyl, tert-butyl, and methoxy could be successfully engaged in the current migration reaction. Among them, a sterically encumbered 2-chloro- phenyl and 2-methylphenyl analogues were appropriate reaction partner, enabling the radical relay alkynyl migration process to provide the corresponding products 3e and 3h in 52% and 50% yields, respectively. Moreover, 2-thienyl analogue 1l was proven to be favorable for this alkynyl migration. Liner n-propyl group (1n) exhibited good compatibility, as evident by the corresponding product 3n was offered in 40% yield. Next, the possible variation in the R¹ substituents attached by a quaternary carbon of 1, 4-enynes was examined. Diverse substituents such as aryl and heteroaryl can all tolerate under the redox-neutral conditions, delivering products 3o~3w in acceptable yields. All tested aryl groups, relative to tertiary alcohol moiety, with varied functionalities and substitution patterns underwent this radical alkynyl migration process, giving access to the corresponding products 3o~3w. Various functional groups, such as chloro, fluoro, methyl, ethyl, tert-butyl, methoxy and trifluoromethyl, all worked well. Alternatively, n-hexyl 1, 4-enyne 1x was readily converted into product 3x in 47% yield. Next, bis(3, 5-dimethyl- phenyl)phosphine oxide (2b) was used as a P-centered radical precursor, which could participate in the P-centered radical relay approach to furnish the corresponding γ-keto- phosphine oxide 3y, albeit with a low yield (Table 2).

Table 2

Table 2. Substrate scope

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To gain more insight into this reaction, radical inhibitors such as 2, 2, 6, 6-tetramethyl-1-piperidinyloxy (TEMPO) and butylhydroxytoluene (BHT) were subjected to the reaction system under the standard conditions (Scheme 3a), and the reaction process was completely suppressed without observation of product 3a. These results indicated that this transformation may include a P-centered radical process (Scheme 2a). The removal of the methyl from the terminal olefin unit led to a complex reaction system under the standard conditions, showing that the methyl group linked to the olefin unit was crucial for this transformation (Scheme 2b).

Scheme 2

Scheme 2. Control experiments

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On the basis of the above results and previous reports, ^[16] a reasonable mechanism is depicted in Scheme 3. Initially, diphenylphosphine oxide is oxidized by Ag(I) to form radical intermediate A, together with Ag(0). The addition of radical A to the terminal alkene unit of 1, 4-enynes 1 provides radical intermediate B, followed by 3-exo-dig cyclization ("anti-Baldwin" rules) and alkynyl migration (the homolysis of C—C bond) to produce hydroxyalkyl radical D. Finally, a single electron oxidation of the intermediate D leads to the carbon cation E, which releases a proton to give the final products 3.

3. Conclusions

In summary, starting from easily preformed 1, 4-enynes and diarylphosphine oxides, a silver-mediated alkynyl- phosphonation of unactivated olefins have been developed for the synthesis of a wide range of γ-ketophosphine oxides through radical intramolecular 1, 2-alkynyl migration of 1, 4-enynes. The reaction proceeded with sequential P-centered radical addition to vinyl unit, 3-exo-dig cyclization and 1, 2-alkynyl migration, resulting in the multiple bond-forming events including C—P and C—C bonds in a one-pot manner. Further application of this attractive radical 1, 2-alkynyl migration strategy will be conducted in due course.

Scheme 3

Scheme 3. Plausible reaction mechanism

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4. Experimental section

4.1 General information

¹H NMR (¹³C NMR, ³¹P NMR) spectra were measured on a Bruker DPX 400 MHz spectrometer in CDCl₃ (DMSO-d₆). HRMS (ESI) was determined by using a microTOF-QII HRMS/MS instrument (BRUKER).

4.1.1 General procedure for the synthesis of compounds 3a~3y

In a Schlenk tube, 1, 4-enynes, (0.2 mmol), diphenylphosphine oxide (0.2 mmol), Ag₂O (0.6 mmol), acetonitrile (3.0 mL), and H₂O (0.5 mL) were continuously added. Then the tube was sealed with a Teflon lined cap and stirred at 100 ℃ for 10 h until complete consumption of starting material as monitored by thin-layer chromatography (TLC, petroleum ether/ethyl acetate, V:V＝1:1) analysis. Then the solvent was evaporated under reduced pressure, and the crude products were purified by flash column chromatography on silica gel with petroleum ether/EtOAc (V:V＝5:1) as the eluent to give the desired products 3a~3y.

2-[(Diphenylphosphoryl)methyl]-1-(4-fluorophenyl)-2-methyl-4-phenylbut-3-yn-1-one (3a): Yellow oil. 59.7 mg, 64% yield. ¹H NMR (400 MHz, CDCl₃) δ: 8.36~8.30 (m, 2H), 7.88~7.78 (m, 4H), 7.48~7.41 (m, 6H), 7.28 (d, J＝7.6 Hz, 1H), 7.24~7.18 (m, 2H), 7.15~7.10 (m, 2H), 6.98 (d, J＝7.2 Hz, 2H), 3.49~3.41 (m, 1H), 2.98~2.88 (m, 1H), 1.97 (s, 3H); ¹³C NMR (100 MHz, CDCl₃) δ: 197.5 (d, ⁷J_C_—_P＝6.7 Hz), 165.2 (d, ¹J_C_—_P＝126.4 Hz), 132.6 (d, ⁶J_C_—_F＝9.0 Hz), 131.4, 131.3, 131.0 (d, ⁴J_C_—_P＝9.3 Hz), 130.7 (d, ⁵J_C_—_P＝9.1 Hz), 128.6 (d, ¹¹J_C_—_P＝5.0 Hz), 128.5 (d, ¹⁰J_C_—_P＝5, 2 Hz), 128.3, 127.9, 122.3, 115.0 (d, ³J_C_—_F＝21.6 Hz), 90.5 (d, ⁹J_C_—_P＝6.2 Hz), 88.4, 44.2 (d, ¹²J_C_—_P＝3.4 Hz), 39.0 (d, ²J_C_—_P＝71.8 Hz), 28.7 (d, ⁸J_C_—_P＝6.3 Hz); ³¹P NMR (162 MHz, CDCl₃) δ: 27.53; IR (KBr) ν: 3056, 2927, 2197, 1685, 1598, 1437, 1232, 756, 692 cm^－1; HRMS (ESI) calcd for C₃₀H₂₄FO₂PNa [M+Na]⁺ 489.1396, found 489.1409.

2-[(Diphenylphosphoryl)methyl]-1, 4-bis(4-fluorophen-yl)-2-methylbut-3-yn-1-one (3b): Yellow oil. 65.9 mg, 68% yield. ¹H NMR (400 MHz, CDCl₃) δ: 8.35~8.28 (m, 2H), 7.89~7.77 (m, 4H), 7.50~7.39 (m, 6H), 7.16~7.10 (m, 2H), 6.96~6.87 (m, 4H), 3.50~3.42 (m, 1H), 2.94~2.85 (m, 1H), 1.96 (s, 3H); ¹³C NMR (100 MHz, CDCl₃) δ: 196.6 (d, ⁶J_C_—_P＝8.0 Hz), 163.1, 132.5, 131.4, 131.1 (d, ⁴J_C_—_P＝9.2 Hz), 130.7 (d, ⁵J_C_—_P＝9.1 Hz), 128.5 (d, ³J_C_—_P＝11.7 Hz), 128.2 (d, ²J_C_—_F＝22.3 Hz), 127.8, 127.3, 122.6, 113.2, 91.0 (d, ⁷J_C_—_P＝6.0 Hz), 88.1, 55.5, 43.9 (d, ⁹J_C_—_P＝3.4 Hz), 38.6 (d, ¹J_C_—_P＝72.2 Hz), 28.4 (d, ⁸J_C_—_P＝5.0 Hz); ³¹P NMR (162 MHz, CDCl₃) δ: 27.83; IR (KBr) ν: 3047, 2931, 2166, 1684, 1588, 1497, 1183, 844, 695 cm^－1; HRMS (ESI) calcd for C₃₀H₂₃F₂O₂PNa [M+Na]⁺ 507.1301, found 507.1315.

2-[(Diphenylphosphoryl)methyl]-1-(3-fluorophenyl)-4-(4-fluorophenyl)-2-methylbut-3-yn-1-one (3c): Yellow oil. 59.1 mg, 61% yield. ¹H NMR (400 MHz, CDCl₃) δ: 8.35~8.28 (m, 2H), 7.89~7.77 (m, 4H), 7.50~7.39 (m, 6H), 7.16~7.10 (m, 2H), 6.96~6.87 (m, 4H), 3.50~3.42 (m, 1H), 2.94~2.85 (m, 1H), 1.96 (s, 3H); ¹³C NMR (100 MHz, CDCl₃) δ: 197.4 (d, ¹⁰J_C_—_P＝6.7 Hz), 165.2 (d, ¹J_C_—_F＝252.8 Hz), 162.5 (d, ²J_C_—_F＝248.0 Hz), 133.2 (d, ⁶J_C_—_P＝9.4 Hz), 132.5 (d, ⁹J_C_—_P＝9.1 Hz), 131.4 (d, ¹⁷J_C_—_P＝3.1 Hz), 131.0 (d, ⁷J_C_—_F＝9.2 Hz), 130.7 (d, ⁸J_C_—_F＝9.1 Hz), 128.6 (d, ¹³J_C_—_P＝6.2 Hz), 128.5 (d, ¹¹J_C_—_P＝6.4 Hz), 118.4 (d, ¹⁶J_C_—_F＝3.5 Hz), 115.2 (d, ⁴J_C_—_F＝13.4 Hz), 115.0 (d, ⁵J_C_—_F＝13.1 Hz), 90.2 (d, ¹⁴J_C_—_P＝4.6 Hz), 87.42, 44.1 (d, ¹⁴J_C_—_P＝3.5 Hz), 38.9 (d, ³J_C_—_P＝72.0 Hz), 28.7 (d, ¹²J_C_—_P＝6.4 Hz); ³¹P NMR (162 MHz, CDCl₃) δ: 27.53; IR (KBr) ν: 3027, 2927, 2161, 1683, 1598, 1504, 1183, 844, 695 cm^－1; HRMS (ESI) calcd for C₃₀H₂₃F₂O₂PNa [M+Na]⁺ 507.1301, found 507.1318.

4-(3-Chlorophenyl)-2-((diphenylphosphoryl)methyl)-1-(4-fluorophenyl)-2-methylbut-3-yn-1-on (3d): Yellow oil. 58.1 mg, 58% yield. ¹H NMR (400 MHz, CDCl₃) δ: 8.31~8.20 (m, 2H), 7.83~7.73 (m, 4H), 7.47~7.35 (m, 6H), 7.22~7.17 (m, 1H), 7.12~7.05 (m, 3H), 6.86~6.80 (m, 1H), 6.77~6.66 (m, 1H), 3.47~3.38 (m, 1H), 2.87~2.79 (m, 1H), 1.92 (s, 3H); ¹³C NMR (100 MHz, CDCl₃) δ: 197.3 (d, ⁷J_C_—_P＝6.9 Hz), 166.3 (d, ¹J_C_—_F＝253.2 Hz), 133.8, 132.5 (d, ⁵J_C_—_F＝9.1 Hz), 131.6 (d, ¹⁴J_C_—_F＝3.3 Hz), 131.5 (d, ¹²J_C_—_P＝4.3 Hz), 131.3, 131.0 (d, ⁴J_C_—_P＝9.4 Hz), 130.7 (d, ⁶J_C_—_P＝9.1 Hz), 129.4, 129.2, 128.7 (d, ¹¹J_C_—_P＝4.5 Hz), 128.6 (d, ¹⁰J_C_—_P＝4.8 Hz), 124.0, 115.1 (d, ³J_C_—_F＝21.7 Hz), 91.8 (d, ⁹J_C_—_P＝5.9 Hz), 87.2, 44.2 (d, ¹³J_C_—_P＝3.7 Hz), 38.9 (d, ¹J_C_—_P＝72.0 Hz), 28.8 (d, ⁸J_C_—_P＝6.7 Hz); ³¹P NMR (162 MHz, CDCl₃) δ: 27.64; IR (KBr) ν: 3057, 2928, 2167, 1686, 1598, 1504, 1189, 844, 695 cm^－1; HRMS (ESI) calcd for C₃₀H₂₃ClFO₂PNa [M+Na]⁺ 523.1006, found 523.1021.

4-(2-Chlorophenyl)-2-((diphenylphosphoryl)methyl)-1-(4-fluorophenyl)-2-methylbut-3-yn-1-one (3e): Yellow oil. 52.1 mg, 52% yield. ¹H NMR (400 MHz, CDCl₃) δ: 8.37~8.29 (m, 2H), 7.82~7.71 (m, 4H), 7.40~7.32 (m, 6H), 7.23 (d, J＝8.0 Hz, 1H), 7.15~7.10 (m, 1H), 7.06~6.98 (m, 3H), 6.83~6.77 (m, 1H), 3.46~3.37 (m, 1H), 2.96~2.87 (m, 1H), 1.93 (s, 3H); ¹³C NMR (100 MHz, CDCl₃) δ: 196.9 (d, ⁸J_C_—_P＝6.1 Hz), 165.2 (d, ¹J_C_—_F＝252.8 Hz), 135.7, 133.5, 132.8 (d, ⁶J_C_—_F＝9.0 Hz), 131.4 (d, ¹³J_C_—_F＝2.5 Hz), 131.0 (d, ⁴J_C_—_P＝9.4 Hz), 130.7 (d, ⁵J_C_—_P＝9.2 Hz), 129.4, 128.9, 128.6 (d, ¹¹J_C_—_P＝4.7 Hz), 128.5 (d, ¹⁰J_C_—_P＝4.8 Hz), 126.08, 122.24, 115.0 (d, ³J_C_—_F＝21.7Hz), 95.6 (d, ⁹J_C_—_P＝6.0 Hz), 85.23, 44.4 (d, ¹²J_C_—_P＝3.5 Hz), 39.2 (d, ²J_C_—_P＝71.3 Hz), 28.7 (d, ⁷J_C_—_P＝6.5 Hz); ³¹P NMR (162 MHz, CDCl₃) δ: 27.39; IR (KBr) ν: 3056, 2928, 2264, 1683, 1597, 1485, 1190, 824, 695 cm^－1; HRMS (ESI) calcd for C₃₀H₂₃ClFO₂PNa [M+Na]⁺ 523.1006, found 523.1018.

4-(4-Bromophenyl)-2-[(diphenylphosphoryl)methyl]-1-(4-fluorophenyl)-2-methylbut-3-yn-1-one (3f): Yellow solid; 67.6 mg, 62% yield. m.p. 101~102 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 8.29~8.27 (m, 2H), 7.85~7.76 (m, 4H), 7.48~7.38 (m, 6H), 7.32 (d, J＝8.0 Hz, 2H), 7.13~7.08 (m, 2H), 6.80 (d, J＝8.4 Hz, 2H), 3.49~3.43 (m, 1H), 2.92~2.86 (m, 1H), 1.95 (s, 3H); ¹³C NMR (100 MHz, CDCl₃) δ: 197.2 (d, J＝6.6 Hz), 166.5 (d, ¹J_C_—_F＝252.9 Hz), 163.92 (s), 132.8, 132.5 (d, ⁴J_C_—_P＝8.9 Hz), 131.5, 131.2, 131.0(d, ²J_C_—_P＝9.4 Hz), 130.8(d, ³J_C_—_P＝9.1 Hz), 128.7 (d, ³J_C_—_F＝8 Hz), 128.5 (d, ⁷J_C_—_P＝5.1 Hz), 122.6, 121.2, 115.2 (d, ²J_C_—_F＝21.6 Hz), 91.8 (d, ⁶J_C_—_P＝5.8 Hz), 87.4, 44.2 (d, ⁴J_C_—_F＝3.5 Hz), 39.21 (d, ¹J_C_—_P＝71.9 Hz), 28.7 (d, ⁵J_C_—_P＝6.6 Hz); ³¹P NMR (162 MHz, CDCl₃) δ: 27.21; IR (KBr) ν: 3056, 2928, 2234, 1683, 1485, 1437, 1190, 824, 695 cm^－1; HRMS (ESI) calcd for C₃₀H₂₃BrFO₂PNa [M+Na]⁺ 567.0501, found 567.0514.

2-[(Diphenylphosphoryl)methyl]-1-(4-fluorophenyl)-2-methyl-4-(m-tolyl)but-3-yn-1-one (3g): Yellow oil. 46.1 mg, 48% yield. ¹H NMR (400 MHz, CDCl₃) δ: 8.30~8.24 (m, 2H), 7.83~7.73 (m, 4H), 7.47~7.41 (m, 2H), 7.40~7.36 (m, 4H), 7.10~7.03 (m, 4H), 6.78~6.73 (m, 1H), 6.67 (d, J＝2.0 Hz, 1H), 3.42~3.35 (m, 1H), 2.91~2.83 (m, 1H), 2.24 (s, 3H), 1.91 (s, 3H); ¹³C NMR (100 MHz, CDCl₃) δ: 197.7 (d, ⁷J_C_—_P＝6.8 Hz), 165.2 (d, ¹J_C_—_F＝252.7 Hz), 137.6, 132.6 (d, ⁵J_C_—_F＝9.1 Hz), 132.0, 131.6 (d, ¹⁴J_C_—_F＝3.3 Hz), 131.5, 131.4 (d, ¹³J_C_—_F＝3.4 Hz), 131.1 (d, ⁴J_C_—_F＝9.3Hz), 130.8 (d, ⁶J_C_—_P＝9.1 Hz), 129.2, 128.6 (d, ¹⁰J_C_—_P＝5.1 Hz), 128.5 (d, ¹¹J_C_—_P＝4.9 Hz), 128.5, 128.4, 127.8, 122.2, 115.1 (d, ³J_C_—_F＝21.7 Hz), 90.2 (d, ⁹J_C_—_P＝6.2 Hz), 88.6, 44.2 (d, ¹²J_C_—_P＝3.6 Hz), 39.0 (d, ²J_C_—_P＝71.9 Hz), 28.7(d, ⁸J_C_—_P＝6.4 Hz), 21.2; ³¹P NMR (162 MHz, CDCl₃) δ: 27.64; IR (KBr) ν: 3056, 2924, 2216, 1684, 1505, 1437, 1192, 844, 692 cm^－1; HRMS (ESI) calcd for C₃₁H₂₆FO₂PNa [M+Na]⁺ 503.1552, found 503.1563.

2-[(Diphenylphosphoryl)methyl]-1-(4-fluorophenyl)-2-methyl-4-(o-tolyl)but-3-yn-1-one (3h): Yellow solid; 52.9 mg, 50% yield. m.p. 98~99 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 8.37~8.27 (m, 2H), 7.87~7.75 (m, 4H), 7.45~7.35 (m, 6H), 7.19~7.15 (m, 1H), 7.13~7.06 (m, 3H), 7.04~6.99 (m, 1H), 6.94~6.89 (m, 1H), 3.50~3.42 (m, 1H), 3.03~2.92 (m, 1H), 2.16 (s, 3H), 1.98 (s, 3H); ¹³C NMR (100 MHz, CDCl₃) δ: 197.6 (d, ⁹J_C_—_P＝6.2 Hz), 165.1 (d, ¹J_C_—_F＝252.6 Hz), 140.1, 132.6 (d, ⁶J_C_—_F＝9.0 Hz), 131.9, 131.7 (d, ¹³J_C_—_F＝3.1 Hz), 131.4 (d, ¹⁴J_C_—_P＝2.5 Hz), 130.9 (d, ⁴J_C_—_P＝9.2Hz), 130.7 (d, ⁵J_C_—_P＝9.1 Hz), 129.18, 128.5 (d, ¹⁰J_C_—_P＝4.1 Hz), 128.4 (d, ¹¹J_C_—_P＝4.1 Hz), 128.3, 125.2, 122.1, 115.0 (d, ³J_C_—_F＝21.5 Hz), 94.3 (d, ⁷J_C_—_P＝6.4 Hz), 87.5, 44.5 (d, ¹²J_C_—_P＝4.1 Hz), 39.5 (d, ²J_C_—_P＝71.5 Hz), 28.8 (d, ⁸J_C_—_P＝6.4 Hz), 20.5; ³¹P NMR (162 MHz, CDCl₃) δ: 27.29; IR (KBr) ν: 3057, 2927, 2220, 1686, 1598, 1437, 1190, 846, 696 cm^－1; HRMS (ESI) calcd for C₃₁H₂₆FO₂PNa [M+Na]⁺ 503.1552, found 503.1567.

2-[(Diphenylphosphoryl)methyl]-4-(4-ethylphenyl)-1-(4-fluorophenyl)-2-methylbut-3-yn-1-one (3i): Yellow oil. 54.4 mg, 55% yield. ¹H NMR (400 MHz, CDCl₃) δ: 8.31~8.24 (m, 2H), 7.84~7.72 (m, 4H), 7.46~7.35 (m, 6H), 7.09~6.97 (m, 4H), 6.87~6.80 (m, 2H), 3.42~3.33 (m, 1H), 2.92~2.84 (m, 1H), 2.62~2.56 (m, 2H), 1.91 (s, 3H), 1.19 (t, J＝7.6 Hz, 3H); ¹³C NMR (100 MHz, CDCl₃) δ: 197.7 (d, ⁷J_C_—_P＝6.8 Hz), 165.2 (d, ¹J_C_—_F＝252.6 Hz), 144.8, 132.6 (d, ⁵J_C_—_F＝9.2 Hz), 131.7 (d, ¹³J_C_—_P＝3.3 Hz), 131.4 (d, ¹⁴J_C_—_F＝3.1 Hz), 131.38, 131.1 (d, ⁴J_C_—_P＝9.4 Hz), 130.8 (d, ⁶J_C_—_P＝9.1 Hz), 128.6 (d, ¹⁰J_C_—_P＝5.1 Hz), 128.5 (d, ¹¹J_C_—_P＝5.1 Hz), 127.52, 119.59, 115.0 (d, ³J_C_—_F＝21.5 Hz), 89.9 (d, ⁸J_C_—_P＝6.4 Hz), 88.58, 44.3 (d, ¹²J_C_—_P＝3.6 Hz), 39.0 (d, ²J_C_—_P＝71.9 Hz), 28.85, 28.7 (d, ⁹J_C_—_P＝6.3 Hz), 15.45; ³¹P NMR (162 MHz, CDCl₃) δ: 27.24; IR (KBr) ν: 3052, 2915, 2210, 1685, 1598, 1422, 1187, 846, 695 cm^－1; HRMS (ESI) calcd for C₃₂H₂₈F- O₂PNa [M+Na]⁺ 517.1709, found 517.1719.

4-[4-(tert-Butyl)phenyl]-2-[(diphenylphosphoryl)methyl]- 1-(4-fluorophenyl)-2-methylbut-3-yn-1-one (3j): Yellow oil. 53.3 mg, 51% yield. ¹H NMR (400 MHz, CDCl₃) δ: 8.31~8.23 (m, 2H), 7.83~7.71 (m, 4H), 7.45~7.34 (m, 6H), 7.20~7.14 (m, 2H), 7.10~7.03 (m, 2H), 6.91~6.84 (m, 2H), 3.41~3.32 (m, 1H), 2.93~2.84 (m, 1H), 1.91 (s, 3H), 1.28 (s, 9H); ¹³C NMR (100 MHz, CDCl₃) δ: 197.6 (d, ⁷J_C_—_P＝6.8 Hz), 165.2 (d, ¹J_C_—_F＝252.9 Hz), 151.7 (d, ¹⁰J_C_—_P＝6.3 Hz), 132.6 (d, ⁵J_C_—_F＝9.0 Hz), 131.7 (d, ¹⁴J_C_—_P＝3.3 Hz), 131.4(3) (d, ¹⁵J_C_—_F＝2.9 Hz), 131.4(8) (d, ¹⁶J_C_—_P＝2.9 Hz), 131.2, 131.1 (d, ⁶J_C_—_P＝7.2 Hz), 130.8 (d, ⁴J_C_—_P＝9.2 Hz), 128.6 (d, ¹²J_C_—_P＝5.2 Hz), 128.5 (d, ¹¹J_C_—_P＝5.3 Hz), 124.9, 119.4, 115.0 (d, ³J_C_—_F＝21.6 Hz), 90.0 (d, ⁸J_C_—_P＝6.7 Hz), 88.5, 44.3 (d, ¹³J_C_—_P＝3.6 Hz), 39.1 (d, ²J_C_—_P＝71.7 Hz), 34.8, 31.2, 28.7 (d, ⁹J_C_—_P＝6.4 Hz); ³¹P NMR (162 MHz, CDCl₃) δ: 27.47; IR (KBr) ν: 3059, 2920, 2226, 1680, 1489, 1448, 1175, 755, 698 cm^－1; HRMS (ESI) calcd for C₃₄H₃₂FO₂PNa [M+Na]⁺ 545.2022, found 545.2045.

2-[(Diphenylphosphoryl)methyl]-1-(4-fluorophenyl)-4-(4- methoxyphenyl)-2-methylbut-3-yn-1-one (3k): Yellow oil. 44.7 mg, 45% yield. ¹H NMR (400 MHz, CDCl₃) δ: 8.34~8.31 (m, 2H), 7.89~7.78 (m, 4H), 7.50~7.43 (m, 6H), 7.13~7.09 (m, 2H), 6.92 (d, J＝8.8 Hz, 2H), 6.75 (d, J＝8.8 Hz, 2H), 3.81 (s, 3H), 3.47~3.41 (m, 1H), 2.95~2.89 (m, 1H), 1.95 (s, 3H); ¹³C NMR (100 MHz, CDCl₃) δ: 197.6, 166.4 (d, ¹J_C_—_F＝252.5), 159.6, 132.8, 132.7 (d, ³J_C_—_F＝8.9), 131.6 (d, ⁴J_C_—_F＝3.1), 131.4, 131.1 (d, ²J_C_—_P＝9.3), 130.8 (d, ³J_C_—_P＝9.1), 128.6 (d, ⁷J_C_—_P＝5.5), 128.4 (d, ⁶J_C_—_P＝5.7), 115.1 (d, ²J_C_—_F＝21.5), 114.5, 113.5, 89.2(d, ⁵J_C_—_P＝6.3), 88.3, 55.3, 44.2 (d, ⁸J_C_—_P＝3.5), 39.4 (d, ¹J_C_—_P＝72.0), 28.7 (d, ⁴J_C_—_P＝6.3). ³¹P NMR (162 MHz, CDCl₃) δ:27.63; IR (KBr) ν: 3055, 2931, 2223, 1682, 1599, 1437, 1249, 832, 695 cm^－1; HRMS (ESI) calcd for C₃₁H₂₆FO₃PNa [M+Na]⁺ 519.1501, found 519.1515.

2-[(Diphenylphosphoryl)methyl]-1-(4-fluorophenyl)-2-methyl-4-(thiophen-2-yl)but-3-yn-1-one (3l): Yellow oil. 43.5 mg, 46% yield. ¹H NMR (400 MHz, CDCl₃) δ: 8.32~8.24 (m, 2H), 7.88~7.76 (m, 4H), 7.51~7.41 (m, 6H), 7.22~7.18 (m, 1H), 7.16~7.10 (m, 2H), 6.92~6.87 (m, 1H), 6.80~6.75 (m, 1H), 3.47~3.39 (m, 1H), 2.96~2.88 (m, 1H), 1.96 (s, 3H); ¹³C NMR (100 MHz, CDCl₃) δ: 197.2 (d, ⁷J_C_—_P＝6.8 Hz), 190.8, 165.2 (d, ¹J_C_—_F＝253.0 Hz), 132.6 (d, ⁶J_C_—_P＝9.1 Hz), 132.0, 131.8, 131.5 (d, ¹³J_C_—_F＝2.6 Hz), 131.5, 131.1 (d, ⁴J_C_—_P＝9.5 Hz), 130.8 (d, ⁵J_C_—_P＝9.2 Hz), 128.6 (d, ¹¹J_C_—_P＝4.6 Hz), 128.5 (d, ¹⁰J_C_—_P＝4.8 Hz), 127.1, 126.7, 122.2, 115.1 (d, ³J_C_—_F＝21.6 Hz), 94.3 (d, ⁹J_C_—_F＝6.3 Hz), 82.0, 44.4 (d, ¹²J_C_—_P＝3.7 Hz), 39.0 (d, ²J_C_—_P＝71.8 Hz), 28.6 (d, ⁸J_C_—_P＝6.6 Hz); ³¹P NMR (162 MHz, CDCl₃) δ: 27.18; IR (KBr) ν: 3057, 2927, 2212, 1682, 1598, 1437, 1233, 844, 695 cm^－1; HRMS (ESI) calcd for C₂₈H₂₂FO₂PSNa [M+Na]⁺ 495.0960, found 495.0976.

1-(4-Chlorophenyl)-2-((diphenylphosphoryl)methyl)-2-methyl-4-phenylbut-3-yn-1-one (3m): Yellow oil. 58.0 mg, 60% yield. ¹H NMR (400 MHz, CDCl₃) δ: 8.23 (d, J＝8.4 Hz, 1H), 7.88~7.76 (m, 1H), 7.41 (d, J＝8.0 Hz, 1H), 7.30~7.24 (m, 1H), 7.23~7.17 (m, 1H), 6.97 (d, J＝7.2 Hz, 1H), 3.51~3.40 (m, 1H), 2.98~2.90 (m, 1H), 1.95 (s, 1H); ¹³C NMR (100 MHz, CDCl₃) δ: 198.0 (d, ⁷J_C_—_P＝6.2 Hz), 138.7, 133.8, 131.47 (d, ¹¹J_C_—_P＝2.2 Hz), 131.5 (d, ⁹J_C_—_P＝3.3 Hz), 131.0 (d, ⁴J_C_—_P＝9.3 Hz), 130.7 (d, ⁵J_C_—_P＝9.1 Hz), 128.6 (d, ³J_C_—_P＝22.8 Hz), 128.5 (d, ¹⁰J_C_—_P＝3.0 Hz), 128.4, 128.2, 128.0, 122.3, 90.4 (d, ²J_C_—_P＝42.6 Hz), 88.4, 44.3 (d, ⁸J_C_—_P＝3.5 Hz), 39.1 (d, ¹J_C_—_P＝71.6 Hz), 28.7 (d, ⁶J_C_—_P＝6.6 Hz); ³¹P NMR (162 MHz, CDCl₃) δ: 27.49; IR (KBr) ν: 3056, 2928, 2165, 1685, 1588, 1437, 1191, 754, 692 cm^－1; HRMS (ESI) calcd for C₃₀H₂₄ClO₂PNa [M+Na]⁺ 505.1100, found 505.1124.

4-[(Diphenylphosphoryl)methyl]-4-methyl-1-phenylno-na-1, 5-diyn-3-one (3n): Yellow oil. 35.1 mg, 40% yield. ¹H NMR (400 MHz, CDCl₃) δ: 7.88~7.75 (m, 4H), 7.51~7.38 (m, 6H), 7.32~7.26 (m, 1H), 7.26~7.20 (m, 2H), 7.09~6.99 (m, 2H), 3.32~3.20 (m, 1H), 3.05~2.94 (m, 1H), 2.92~2.83 (m, 1H), 2.79~2.70 (m, 1H), 1.67 (s, 3H), 1.36~1.33 (m, 2H), 0.93 (t, J＝7.0 Hz, 3H); ¹³C NMR (100 MHz, CDCl₃) δ: 209.4 (d, ⁵J_C_—_P＝4.6 Hz), 131.6, 131.4 (d, ⁷J_C_—_P＝1.5 Hz), 131.1 (d, ¹J_C_—_P＝9.4 Hz), 131.0 (d, ²J_C_—_P＝9.1 Hz), 128.6, 128.5 (d, ⁴J_C_—_P＝4.6 Hz), 128.4, 128.2, 128.0, 127.9, 122.6, 90.0 (d, ³J_C_—_P＝5.1 Hz), 86.9, 45.2 (d, ⁶J_C_—_P＝3.8 Hz) 38.8, 31.4, 23.7, 22.6, 14.1; ³¹P NMR (162 MHz, CDCl₃) δ: 27.50; IR (KBr) ν: 3056, 2928, 2164, 1697, 1488, 1437, 1190, 829, 695 cm^－1; HRMS (ESI) calcd for C₂₉H₂₇O₂PNa [M+Na]⁺ 461.1646, found 461.1658.

4-(4-Chlorophenyl)-2-[(diphenylphosphoryl)methyl]-2-methyl-1-(p-tolyl)but-3-yn-1-one (3o): Yellow oil. 58.6 mg, 59% yield. ¹H NMR (400 MHz, CDCl₃) δ: 8.35~8.31 (m, 2H), 7.87~7.76 (m, 4H), 7.44~7.39 (m, 6H), 7.20~7.16 (m, 1H), 7.13~7.08 (m, 3H), 7.05~7.01 (m, 1H), 6.93 (d, J＝7.2 Hz, 1H), 3.51~3.45 (m, 1H), 3.01~2.95 (m, 1H), 2.17 (s, 3H), 1.98 (s, 3H); ¹³C NMR (100 MHz, CDCl₃) δ: 197.8 (d, ⁶J_C_—_P＝7.6 Hz), 149.6, 134.2 (d, ²J_C_—_P＝15.8 Hz), 132.6, 132.4, 131.5 (d, ⁵J_C_—_P＝8.9 Hz), 131.1 (d, ³J_C_—_P＝9.1 Hz), 130.7 (d, ⁴J_C_—_P＝9.0 Hz), 130.2, 128.7, 128.2, 127.5, 121.0, 91.8 (d, ⁷J_C_—_P＝5.6 Hz), 87.1, 44.1 (d, ⁹J_C_—_P＝3.1 Hz), 38.8(d, ¹J_C_—_P＝72.7 Hz), 28.9, 28.4(d, ⁸J_C_—_P＝4.9 Hz), 15.18; ³¹P NMR (162 MHz, CDCl₃) δ:27.22; IR (KBr) ν: 3055, 2966, 2126, 1682, 1605, 1437, 1183, 829, 695 cm^－1; HRMS (ESI) calcd for C₃₁H₂₆ClO₂PNa [M+Na]⁺ 519.1257, found 519.1271.

4-(4-Chlorophenyl)-2-((diphenylphosphoryl)methyl)-2-methyl-1-(m-tolyl)but-3-yn-1-one (3p): Yellow oil. 50.7 mg, 51% yield. ¹H NMR (400 MHz, CDCl₃) δ: 8.12 (d, J＝8.4 Hz, 2H), 7.85~7.72 (m, 5H), 7.47~7.34 (m, 7H), 7.20 (d, J＝8.0 Hz, 2H), 7.14~7.10 (m, 2H), 6.85~6.82 (m, 2H), 3.42~3.36 (m, 1H), 2.84~2.78 (m, 1H), 2.39 (s, 3H), 1.95 (s, 3H); ¹³C NMR (100 MHz, CDCl₃) δ: 197.8, 143.5, 134.2, 132.7, 132.2, 131.6 (d, ⁹J_C_—_P＝2.9 Hz), 131.5 (d, ⁸J_C_—_P＝3.1 Hz), 131.3 (d, ²J_C_—_P＝9.4 Hz), 130.7 (d, ³J_C_—_P＝d, J＝9.2 Hz), 130.1, 128.8, 128.3, 121.1, 91.8 (d, ⁴J_C_—_P＝6.1 Hz), 87.2 (d, ¹⁰J_C_—_P＝2.1 Hz), 44.1 (d, ⁷J_C_—_P＝3.6 Hz), 38.8 (d, ¹J_C_—_P＝71.9 Hz), 28.4 (d, ⁵J_C_—_P＝5.9 Hz), 21.7 (d, ⁶J_C_—_P＝5.4 Hz); ³¹P NMR (162 MHz, CDCl₃) δ: 27.92; IR (KBr) ν: 3055, 2916, 2167, 1680, 1489, 1437, 1183, 827, 692 cm^－1; HRMS (ESI) calcd for C₃₁H₂₆Cl- O₂PNa [M+Na]⁺ 519.1257, found 519.1266.

4-(4-Chlorophenyl)-2-[(diphenylphosphoryl)methyl]-2-methyl-1-(o-tolyl)but-3-yn-1-one (3q): Yellow oil. 53.7 mg, 54% yield. ¹H NMR (400 MHz, CDCl₃) δ: 8.06 (d, J＝7.6 Hz, 1H), 7.86~7.81 (m, 4H), 7.48~7.43 (m, 6H), 7.35~7.31 (m, 1H), 7.26 (d, J＝7.6 Hz, 1H), 7.23~7.19 (m, 1H), 7.15 (d, J＝8.4 Hz, 2H), 6.80 (d, J＝8.0 Hz, 2H), 3.53~3.47 (m, 1H), 2.97~2.91 (m, 1H), 2.46 (s, 3H), 1.84 (s, 3H); ¹³C NMR (100 MHz, CDCl₃) δ: 203.2 (d, ⁸J_C_—_P＝5.6 Hz), 137.3, 136.8, 134.9(d, ²J_C_—_P＝27 Hz), 134.1, 133.9 (d, ³J_C_—_P＝26.9 Hz), 132.6, 131.5, 131.1(d, ⁵J_C_—_P＝9.4 Hz), 130.9 (d, ⁹J_C_—_P＝4.7 Hz), 130.7, 130.2, 128.6 (d, ⁴J_C_—_P＝11.7 Hz), 128.3, 128.2, 124.3, 121.0, 91.5 (d, ⁷J_C_—_P＝6.1 Hz), 86.9, 45.9 (d, ¹⁰J_C_—_P＝3.9 Hz), 38.7 (d, ¹J_C_—_P＝71.7 Hz), 28.3 (d, ⁶J_C_—_P＝7.4 Hz), 20.4; ³¹P NMR (162 MHz, CDCl₃) δ: 27.44; IR (KBr) ν: 3055, 2928, 2152, 1697, 1488, 1437, 1190, 829, 695 cm^－1; HRMS (ESI) calcd for C₃₁H₂₆ClO₂PNa [M+Na]⁺ 519.1257, found 519.1264.

4-(4-Chlorophenyl)-2-[(diphenylphosphoryl)methyl]-1-(4-ethylphenyl)-2-methylbut-3-yn-1-one (3r): Yellow oil. 52.1 mg, 51% yield. ¹H NMR (400 MHz, CDCl₃) δ: 8.21 (d, J＝8.4 Hz, 2H), 7.90~7.85 (m, 2H), 7.82~7.76 (m, 2H), 7.47~7.39 (m, 6H), 7.28 (d, J＝8.4 Hz, 2H), 7.16 (d, J＝8.4 Hz, 2H), 6.88 (d, J＝8.4 Hz, 2H), 3.49~3.43 (m, 1H), 2.91~2.85 (m, 1H), 2.74~2.68 (m, 2H), 2.00 (s, 3H), 1.31~1.25 (m, 3H); ¹³C NMR (100 MHz, CDCl₃) δ: 197.8 (d, ⁷J_C_—_P＝7.7 Hz), 149.5, 135.3 (d, ¹J_C_—_P＝269.9 Hz), 134.4(d, ⁶J_C_—_P＝8.3 Hz), 134.1, 133.4, 132.6, 132.4, 131.4 (d, ¹³J_C_—_P＝2.6 Hz), 131.384 (d, ¹²J_C_—_P＝2.7 Hz), 131.1 (d, ⁴J_C_—_P＝9.3 Hz), 130.7 (d, ⁵J_C_—_P＝9.1 Hz), 130.2, 128.6 (d, ³J_C_—_P＝20.1 Hz), 128.5 (d, ¹¹J_C_—_P＝3.2 Hz), 128.2, 127.5, 91.8 (d, ⁸J_C_—_P＝6 Hz), 87.1, 44.2 (d, ¹⁰J_C_—_P＝3.5 Hz), 38.8 (d, ²J_C_—_P＝72.1 Hz), 28.9, 28.3 (d, ⁹J_C_—_P＝5.3 Hz), 15.2; ³¹P NMR (162 MHz, CDCl₃) δ: 27.98; IR (KBr) ν: 3055, 2967, 2122, 1682, 1605, 1437, 1183, 829, 695 cm^－1; HRMS (ESI) calcd for C₃₂H₂₈ClO₂PNa [M+Na]⁺ 533.1413, found 533.1409.

1-[3-(tert-Butyl)phenyl]-4-(4-chlorophenyl)-2-[(diphen-ylphosphoryl)methyl]-2-methylbut-3-yn-1-one (3s): Yellow oil. 55.0 mg, 51% yield. ¹H NMR (400 MHz, CDCl₃) δ: 8.26~8.20 (m, 2H), 7.91~7.85 (m, 2H), 7.82~7.75 (m, 2H), 7.49~7.40 (m, 8H), 7.20~7.15 (m, 2H), 6.91~6.86 (m, 2H), 3.49~3.41 (m, 1H), 2.92~2.83 (m, 1H), 2.01 (s, 3H), 1.38 (s, 9H); ¹³C NMR (100 MHz, CDCl₃) δ: 197.8 (d, ⁶J_C_—_P＝6.8 Hz), 156.3, 132.6, 131.1 (d, ²J_C_—_P＝9.2 Hz), 130.6 (d, ³J_C_—_P＝9.0 Hz), 129.9, 128.6 (d, ⁵J_C_—_P＝8.3 Hz), 128.5 (d, ⁴J_C_—_P＝8.5 Hz), 128.2, 125.0, 121.1, 91.8 (d, ⁷J_C_—_P＝6.1 Hz), 87.0, 44.1 (d, ⁹J_C_—_P＝3.5 Hz), 38.7 (d, ¹J_C_—_P＝72.2 Hz), 35.1, 31.1, 28.3 (d, ⁸J_C_—_P＝5.1 Hz); ³¹P NMR (162 MHz, CDCl₃) δ: 27.68; IR (KBr) ν: 3055, 2963, 2146, 1682, 1603, 1437, 1189, 828, 695 cm^－1; HRMS (ESI) calcd for C₃₄H₃₂ClO₂PNa [M+Na]⁺ 561.1726, found 561.1714.

4-(4-Chlorophenyl)-2-[(diphenylphosphoryl)methyl]-1-(3-methoxyphenyl)-2-methylbut-3-yn-1-one (3t): Yellow oil. 45.1 mg, 44% yield. ¹H NMR (400 MHz, CDCl₃) δ: 8.38~8.31 (m, 2H), 7.92~7.79 (m, 4H), 7.48~7.38 (m, 6H), 7.29~7.24 (m, 1H), 7.23~7.17 (m, 2H), 7.01~6.91 (m, 4H), 3.89 (s, 3H), 3.46~3.39 (m, 1H), 2.93~2.85 (m, 1H), 2.02 (s, 3H); ¹³C NMR (100 MHz, CDCl₃) δ: 197.6 (d, ⁷J_C_—_P＝6.6 Hz), 165.1 (d, ¹J_C_—_P＝252.6 Hz), 138.4, 132.6 (d, ⁶J_C_—_P＝7.9 Hz), 131.4, 131.2, 131.1 (d, ⁴J_C_—_P＝9.3 Hz), 130.7 (d, ⁵J_C_—_P＝9.1 Hz), 128.7, 128.6 (d, ⁹J_C_—_P＝5.0 Hz), 128.5 (d, ⁸J_C_—_P＝5.1 Hz), 119.3, 115.0 (d, ³J_C_—_P＝21.6 Hz), 89.8 (d, ¹J_C_—_P＝6.3 Hz), 88.5, 44.2 (d, ¹¹J_C_—_P＝3.6 Hz), 39.0 (d, ²J_C_—_P＝71.8 Hz), 28.7 (d, ¹⁰J_C_—_P＝4.2 Hz), 21.5; ³¹P NMR (162 MHz, CDCl₃) δ: 27.55; IR (KBr) ν: 2924, 2220, 1682, 1598, 1437, 1233, 1189, 816, 695 cm^－1; HRMS (ESI) calcd for C₃₁H₂₆ClO₃PNa [M+Na]⁺ 535.1206, found 535.1215.

1, 4-Bis(4-chlorophenyl)-2-[(diphenylphosphoryl)meth-yl]-2-methylbut-3-yn-1-one (3u): Yellow solid; 66.2 mg, 64% yield. m.p. 111~112 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 8.19 (d, J＝8.4 Hz, 2H), 7.86~7.75 (m, 4H), 7.47~7.36 (m, 8H), 7.16 (d, J＝8.4 Hz, 2H), 6.86 (d, J＝8.4 Hz, 2H), 3.51~3.40 (m, 1H), 2.95~2.85 (m, 1H), 1.93 (s, 3H); ¹³C NMR (100 MHz, CDCl₃) δ: 197.8 (d, ⁵J_C_—_P＝6.2 Hz), 138.7, 134.9, 134.5, 134.4, 133.9, 133.7, 133.5, 132.6, 131.5 (d, ⁹J_C_—_P＝1.7 Hz), 131.2, 131.0 (d, ²J_C_—_P＝9.2 Hz), 130.7 (d, ³J_C_—_P＝9.0 Hz), 128.6 (d, ⁷J_C_—_P＝3.3 Hz), 128.5 (d, ⁷J_C_—_P＝3.5 Hz), 128.2 (d, ⁶J_C_—_P＝3.8 Hz), 120.8, 91.5, 91.4, 87.4, 44.2 (d, ⁸J_C_—_P＝3.5 Hz), 39.0 (d, ¹J_C_—_P＝71.6 Hz), 28.7 (d, ⁴J_C_—_P＝6.7 Hz); ³¹P NMR (162 MHz, CDCl₃) δ: 27.40; IR (KBr) ν: 3056, 2928, 2156, 1685, 1589, 1437, 1191, 829, 695 cm^－1; HRMS (ESI) calcd for C₃₀H₂₃Cl₂O₂PNa [M+Na]⁺ 539.0710, found 539.0717.

4-(4-Chlorophenyl)-2-((diphenylphosphoryl)methyl)-2-methyl-1-(4-(trifluoromethyl)phenyl)but-3-yn-1-one (3v): Yellow oil. 74.9 mg, 68% yield. ¹H NMR (400 MHz, CDCl₃) δ: 8.31 (d, J＝8.4 Hz, 2H), 7.86~7.76 (m, 4H), 7.72 (d, J＝8.4 Hz, 2H), 7.50~7.40 (m, 6H), 7.19 (d, J＝8.4 Hz, 2H), 6.85 (d, J＝8.4 Hz, 2H), 3.54~3.46 (m, 1H), 2.99~2.90 (m, 1H), 1.93 (s, 3H); ¹³C NMR (100 MHz, CDCl₃) δ: 199.1 (d, ⁵J_C_—_P＝5.1 Hz), 139.1, 134.5, 132.5, 131.6 (d, ¹⁰J_C_—_P＝2.2 Hz), 131.5 (d, ¹¹J_C_—_P＝2.1 Hz), 131.0, 130.8 (d, ⁶J_C_—_P＝4.1 Hz), 130.7, 129.1, 128.7 (d, ²J_C_—_P＝8.9 Hz), 128.6 (d, ¹²J_C_—_P＝2.0 Hz), 128.3, 124.9 (d, ⁸J_C_—_F＝3.7 Hz), 122.3, 120.6, 91.1 (d, ⁴J_C_—_F＝6.0 Hz), 87.5, 44.5 (d, ⁸J_C_—_P＝3.3 Hz), 39.2 (d, ¹J_C_—_P＝71.5 Hz), 28.8 (d, ³J_C_—_P＝7.5 Hz); ³¹P NMR (162 MHz, CDCl₃) δ: 27.41; IR (KBr) ν: 3056, 2930, 2196, 1693, 1498, 1437, 1325, 1119, 694 cm^－1; HRMS (ESI) calcd for C₃₁H₂₃Cl- F₃O₂PNa [M+Na]⁺ 573.0974, found 573.0981.

4-(4-Chlorophenyl)-2-((diphenylphosphoryl)methyl)-2-methyl-1-(thiophen-2-yl)but-3-yn-1-one (3w): Yellow oil. 44.0 mg, 45% yield. ¹H NMR (400 MHz, CDCl₃) δ: 8.28 (d, J＝3.6 Hz, 1H), 7.90~7.78 (m, 4H), 7.66 (d, J＝4.8 Hz, 1H), 7.51~7.43 (m, 3H), 7.40 (s, 3H), 7.20 (d, J＝8.4 Hz, 2H), 7.15~7.11 (m, 1H), 6.96 (d, J＝8.4 Hz, 2H), 3.43~3.35 (m, 1H), 2.91~2.81 (m, 1H), 2.03 (s, 3H); ¹³C NMR (100 MHz, CDCl₃) δ: 190.7 (d, ⁴J_C_—_P＝8.5 Hz), 139.9, 134.6, 134.3 (d, ⁵J_C_—_P＝6.4 Hz), 132.7, 131.5 (d, ¹⁰J_C_—_P＝2.2 Hz), 131.4 (d, ⁹J_C_—_P＝2.4 Hz), 131.2 (d, ³J_C_—_P＝9.0 Hz), 130.6 (d, ²J_C_—_P＝9.2Hz), 128.7, 128.5 (d, ⁸J_C_—_P＝4.5 Hz), 128.4, 128.2, 127.8, 120.8, 91.7 (d, ⁶J_C_—_P＝5.2 Hz), 87.3, 44.4 (d, J＝3.3 Hz), 38.0 (d, ¹J_C_—_P＝72.4 Hz), 28.8 (d, ⁷J_C_—_P＝5.0 Hz); ³¹P NMR (162 MHz, CDCl₃) δ: 28.01; IR (KBr) ν: 3056, 2925, 2218, 1658, 1498, 1409, 1190, 829, 695 cm^－1; HRMS (ESI) calcd for C₂₈H₂₂ClO₂PSNa [M+Na]⁺ 511.0664, found 511.0653.

3-((Diphenylphosphoryl)methyl)-3-methyl-1-phenyldec-1-yn-4-one (3x): Yellow oil. 54.0 mg, 47% yield. ¹H NMR (400 MHz, CDCl₃) δ: 7.83~7.71 (m, 4H), 7.42~7.39 (m, 6H), 7.23~7.17 (m, 3H), 7.03~6.96 (m, 2H), 3.25~3.18 (m, 1H), 2.97~2.91 (m, 1H), 2.86~2.80 (m, 1H), 2.74~2.68 (m, 1H), 2.22~2.17 (m, 1H), 2.02 (s, 1H), 1.74 (s, 1H), 1.63 (s, 3H), 1.29~1.26 (m, 6H), 0.88~0.85 (m, 3H); ¹³C NMR (100 MHz, CDCl₃) δ: 209.4 (d, ¹³J_C_—_P＝4.7 Hz), 134.8 (d, ³J_C_—_P＝20.2 Hz), 133.8 (d, ¹J_C_—_P＝30.2 Hz), 131.5 (d, ⁴J_C_—_P＝11.5 Hz), 131.4 (d, ¹⁵J_C_—_P＝3.5 Hz), 131.1 (d, ⁵J_C_—_P＝9.4 Hz), 130.9 (d, ⁶J_C_—_P＝9.1 Hz), 128.6 (d, ¹⁰J_C_—_P＝7.5 Hz), 128.4 (d, ⁹J_C_—_P＝7.6 Hz), 128.1 (d, ²J_C_—_P＝23.2 Hz), 122.6 (s), 90.1 (d, ¹¹J_C_—_P＝5.1 Hz), 86.8 (s), 45.2 (d, ¹⁴J_C_—_P＝3.8 Hz), 38.8 (s), 38.4 (s), 37.7 (s), 31.8 (s), 28.9 (s), 28.1 (d, ⁸J_C_—_P＝8.9 Hz), 24.0 (s), 22.6 (s), 14.1 (s); ³¹P NMR (162 MHz, CDCl₃) δ: 27.70; IR (KBr) ν: 3055, 2922, 2361, 1717, 1437, 1187, 1118, 821, 692 cm^－1; HRMS (ESI) calcd for C₃₀H₃₃O₂PNa [M+Na]⁺ 479.2116, found 479.2109.

2-([Bis(3, 5-dimethylphenyl)phosphoryl)methyl]-2-me-thyl-1, 4-diphenylbut-3-yn-1-one (3y): Yellow oil. 31.3 mg, 31% yield. ¹H NMR (400 MHz, CDCl₃) δ: 8.30 (d, J＝7.6 Hz, 2H), 7.57~7.50 (m, 2H), 7.49~7.43 (m, 3H), 7.38 (d, J＝11.6 Hz, 2H), 7.26 (d, J＝7.6 Hz, 1H), 7.22~7.17 (m, 2H), 7.08 (s, 1H), 6.99 (d, J＝6.8 Hz, 3H), 3.46~3.38 (m, 1H), 2.93~2.83 (m, 1H), 2.29 (d, J＝14.8 Hz, 12H), 2.02 (s, 3H); ¹³C NMR (100 MHz, CDCl₃) δ: 198.8 (d, ⁶J_C_—_P＝7.8 Hz), 138.2, 138.1 (d, ¹¹J_C_—_P＝2.1 Hz), 138.0, 135.3, 134.2 (d, ⁴J_C_—_P＝19.8 Hz), 133.1 (d, ¹⁰J_C_—_P＝2.7 Hz), 132.4, 131.4, 129.9, 128.7 (d, ⁵J_C_—_P＝9.2 Hz), 128.2, 128.1 (d, ¹²J_C_—_P＝1.3 Hz), 128.1, 127.8 (d, ³J_C_—_P＝20.5 Hz), 122.6, 90.6 (d, ¹J_C_—_P＝76.3 Hz), 88.2, 44.2 (d, ⁹J_C_—_P＝3.4 Hz), 38.5 (d, ²J_C_—_P＝71.3 Hz), 29.7, 28.1 (d, ⁷J_C_—_P＝4.9 Hz), 21.3 (d, ⁸J_C_—_P＝4.0 Hz); ³¹P NMR (162 MHz, CDCl₃) δ: 28.49; IR (KBr) ν: 3051, 2920, 2178, 1685, 1598, 1446, 1185, 850, 691 cm^－1; HRMS (ESI) calcd for C₃₄H₃₃O₂PNa [M+Na]⁺ 527.2116, found 527.2122.

Supporting Information ¹H NMR and ¹³C NMR of all new compounds 3a~3x. The Supporting Information is available free of charge via the Internet at http://sioc-journal.cn/.

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Scheme 1 Profiles of radical-mediated functionalization of alkenes

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Scheme 2 Control experiments

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Scheme 3 Plausible reaction mechanism

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Table 1. Optimization of reaction conditions^a


Entry	Ag salt (equiv.)	Solvent	t/℃	Yield^b/%
1	AgNO₃ (2.0)	CH₃CN/H₂O	80	17
2	AgOAc (2.0)	CH₃CN/H₂O	80	6
3	Ag₂CO₃ (2.0)	CH₃CN/H₂O	80	26
4	Ag₂O (2.0)	CH₃CN/H₂O	80	39
5	Ag₂O (2.0)	DCE/H₂O	80	Trace
6	Ag₂O (2.0)	MeOH/H₂O	80	20
7	Ag₂O (2.0)	DMF/H₂O	80	20
8	Ag₂O (2.0)	1, 4-Dioxane/H₂O	80	17
9	Ag₂O (1.0)	CH₃CN/H₂O	80	18
10	Ag₂O (3.0)	CH₃CN/H₂O	80	53
11	Ag₂O (4.0)	CH₃CN/H₂O	80	53
12	Ag₂O (3.0)	CH₃CN/H₂O	90	57
13	Ag₂O (3.0)	CH₃CN/H₂O	100	64
14	Ag₂O (3.0)	CH₃CN/H₂O	110	63
15	Ag₂O (3.0)	CH₃CN	100	45
^a Reaction conditions: 1a (0.2 mmol), 2a (0.2 mmol), silver salt, organic solvent (3.0 mL), H₂O (0.5 mL). ^b Isolated yield based on 1a.

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Table 2. Substrate scope

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