Copper-Catalyzed C−P Bond Construction via Direct Coupling of Phenylboronic Acids with H-Phosphonate Diesters

Zhuang, Rongqiang; Xu, Jian; Cai, Zhenshi; Tang, Guo; Fang, Meijuan; Zhao, Yufen

doi:10.1021/ol200465z

Cited by 184 publications

(94 citation statements)

References 81 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The crude residue was purified by column chromatograph (hexane-ethyl acetate) on silica gel to give arylphosphonates (10, 14-22). The products [10,37) 14, 37) 38) ] were colorless oil, and were confirmed by comparison of NMR data and MS spectra with that in the literature.…”

Section: Methodssupporting

confidence: 72%

Pd-Catalyzed P-Arylation of Triarylantimony Dicarboxylates with Dialkyl H-Phosphites without a Base: Synthesis of Arylphosphonates

Matsumura

Dong

Kakusawa

et al. 2015

CHEMICAL & PHARMACEUTICAL BULLETIN

View full text Add to dashboard Cite

The reaction of triarylantimony diacetates [Ar 3 Sb(OAc) 2 ] with dialkyl H-phosphites [H-PO(OR)2] in the presence of a Pd(PPh 3 ) 4 (5 mol%) catalyst led to the formation of arylphosphonates in moderate to excellent yield under base-free conditions. This reaction is the first example of carbon-phosphorus bond formation by using an organoantimony compound as a pseudo-halide.Key words Hirao-type P-arylation; triarylantimony diacetate; arylphosphonate; dialkyl H-phosphite; basefree reaction Phosphorus-carbon (P-C) bond formation for the synthesis of organophosphorus compounds is a fundamental and significant research topic in organic synthesis, materials, and biology.1-6) Among these, the transition-metal-catalyzed crosscoupling reaction is one of the most practical methods in modern organic syntheses. [7][8][9] With regard to the synthesis of arylphosphonates, the Pd-catalyzed cross-coupling reactions of aryl halides with dialkyl H-phosphites (i.e., Hirao P-arylation) have proved to be a powerful method. [10][11][12][13][14][15][16][17][18][19][20][21] The general procedure of these P-arylations involves a Pd-phosphine complex as the catalyst with the use of a stoichiometric or an excess amount of a base. Recently, different aryl substances were investigated for their reactivity with phosphorus agents. Sulfonates, 22,23) diaryliodonium salts, 24) arylboronic acids, 25) aryldiazonium salts, 26) and triarylbismuthanes 27) have been reported to be useful for P-C bond formation as the arylating reagents with dialkyl H-phosphites; however, a base and/or an additive was required for the transformation.On the other hand, Pd-catalyzed cross-coupling reactions using organoantimony compounds have recently been the focus of attention. Triarylantimony dicarboxylates act as effective arylating agents in Pd-catalyzed C-C(Ar) bond formation reactions such as [28][29][30] 31) and Hiyama-type 32) reactions. Over the past few years, we have also found that they are an efficient aryl donors in base-free Suzuki-type reactions and copper-and base-free Sonogashira-type reactions. [33][34][35] Moreover, base-free Miyaura-type cross-coupling reactions for boron-carbon (B-C) bond formation using triarylantimony diacetates and tetra(alkoxo) diborons afforded the corresponding arylboronates.36) As a continuation of our studies on heteroatom-carbon bond formation, we now report a novel Pd-catalyzed Hirao-type P-arylation of a pentavalent organoantimony compound, triarylantimony diacetate, with dialkyl H-phosphites afford to the corresponding arylphosphonates without using any base. Results and DiscussionWe initially focused our attention on the determination of the optimum conditions for the P-arylation of organoantimony(V) and bismuth(V) compounds (1a-8) with diethyl phosphite (9a) without using a base. The results including the search for active substrates, optimum amount of phosphorus reagent and suitable catalysts for the reaction are summarized in Table 1. The progress of the reaction was monitored by gas-liquid chromatography (GLC) an...

show abstract

Section: Methodssupporting

confidence: 72%

Pd-Catalyzed P-Arylation of Triarylantimony Dicarboxylates with Dialkyl H-Phosphites without a Base: Synthesis of Arylphosphonates

Matsumura

Dong

Kakusawa

et al. 2015

CHEMICAL & PHARMACEUTICAL BULLETIN

View full text Add to dashboard Cite

show abstract

“…Zhuang and co-workers have reported the first example of cross coupling secondary H-phosphonate diesters using catalytic amounts of copper(II)oxide and phenanthroline catalyst in the presence of excess amine base under an oxygen atmosphere to afford aryl phosphonates. 414 Phenol and diaryl ether side-products arising from competing oxidation of the arylboronic acids to the phenol and O-arylation were detected. Notably, the yields decreased from 96% to 56% when the reaction was performed under pure oxygen instead of air.…”

Section: Reaction Of Carbanions and Carbanion Equivalentsmentioning

confidence: 98%

Aerobic Copper-Catalyzed Organic Reactions

et al. 2013

View full text Add to dashboard Cite

24 peroxide [Cu I (pyr)(tpb)] 10 mol % TBHP, 1 atm O 2 , 1:2 AcOH/pyr, rt, 24 h ∼2.5 26 74 g 35 25 n-hexane aldehyde CuCl 2 , 18-crown-6 1 atm O 2 , MeCHO, CH 2 Cl 2 , 70 °C, 24 h 2.4 91 h 9 34a 26 n-decane aldehyde Cu II Cl 16 Pc-AM(PS) 3 equiv of PhCHO, MeCN, 1 atm O 2 , 50 °C 15.4 100 i 61 a See Chart 2 for ligand structures. b Also 28% cyclohexene. c Also 26% cyclohexene. d Mixture of alcohol and hydroperoxide. e Remainder of product is cyclohexene. f Approximately 93:7 of 1-adamantol/2-adamantol. g Approximately 98:2 of 1-adamantol/2-adamantol. h Afforded oxidation products in an approximately 1:1 ratio at the 2-and 3-positions. i Mixture of decanones.

show abstract

“…Additional band at near 1040 cm -1 is due to P-O-C groups. Moreover, important peaks between 1375 and 1467 cm -1 assigned to the P-C linkage are observed [12][13][14][15][16]. Moreover, they all have methyl bands.…”

Section: Resultsmentioning

confidence: 99%