Rhodium-Catalyzed Regio- and Stereoselective Addition of Diphenylphosphine Oxide to Alkynes

Han, Li‐Biao; Zhao, Chang‐Qiu; Tanaka, Masato

doi:10.1021/jo010337z

Cited by 111 publications

(39 citation statements)

References 25 publications

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“…The catalytic activity of this heterogeneous rhodium complex catalyst is comparable to that of homogeneous RhCl 3 . For example, the hydrophosphinylation of 1-octyne in the presence of 3 mol% of MCM-41-2P-RhCl 3 in toluene at 80°C under Ar for 4 h gave a 90% yield of the addition product 3a (entry 1), the same reaction in the presence of 3 mol% RhCl 3 in toluene at 80°C under Ar for 3 h gave 3a in 91% yield [21]. Under the above reaction conditions, aromatic terminal alkynes reacted efficiently with HP(O)Ph 2 affording the corresponding (E)-alkenylphosphine oxides 3c-3g in good to high yields (entries 3-7).…”

Section: Resultsmentioning

confidence: 99%

“…Transitionmetal-catalyzed addition of an P-H bond to alkynes is a straightforward method for the generation of alkenylphosphorus compounds [16][17][18][19][20], but this transformation always results in a mixture of E/Z configurations, and it is difficult to obtain one single product. Han et al [21] described a rhodium-catalyzed regio-and stereoselective hydrophosphinylation of alkynes with Ph 2 P(O)H, which provides a new convenient and clean method for the preparation of (E)-alkenylphosphine oxides. However, industrial applications of homogeneous rhodium complexes remain a challenge because they are expensive, cannot be recycled, and difficult to separate from the product mixture, which is a particularly significant drawback for their application in the pharmaceutical industry.…”

Section: Introductionmentioning

confidence: 99%

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Diphosphino-Functionalized MCM-41-Immobilized Rhodium Complex: A Highly Efficient and Recyclable Catalyst for the Hydrophosphinylation of Terminal Alkynes

et al. 2012

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Diphosphino-functionalized MCM-41-immobilized rhodium complex (MCM-41-2P-RhCl 3 ) was conveniently synthesized from commercially available and cheap c-aminopropyltriethoxysilane via immobilization on mesoporous MCM-41, followed by reacting with diphenylphosphinomethanol and rhodium chloride. It was found that this heterogeneous rhodium complex is a highly efficient catalyst for the hydrophosphinylation of terminal alkynes with diphenylphosphine oxide and can be recovered and recycled by a simple filtration of the reaction solution and used for at least 10 consecutive trials without any decreases in activity.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Diphosphino-Functionalized MCM-41-Immobilized Rhodium Complex: A Highly Efficient and Recyclable Catalyst for the Hydrophosphinylation of Terminal Alkynes

et al. 2012

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“…9) [17] . 该 Rh 催化剂适用于一系列的炔烃, 而且反应中催化活性非常好: 1-辛炔和叔丁基乙炔在室温下反应 40 min 即可高收率的得到产物, 官能团化的炔烃在室温或者 60 ℃的温和条件下只需反应 2～ 12 h, 最不活泼的内炔烃也只需在 100 ℃反应 2 h. 该反应与上述零价钯催化的反应 [10] 类似, 因此我们也提出…”

Section: 钯催化剂unclassified

Transition Metal-Catalyzed Transformations of P(O)—H Bonds

Xu¹,

Zhao²,

Zhou³

et al. 2012

Chin. J. Org. Chem.

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Organophosphorus compounds are of high importance in organic synthesis, catalysis, biochemistry, pharmaceuticals, and material science. In this account, we summarize our recent studies on transition metal-catalyzed transformations of P(O)-H compounds, mainly the regio-and stereo-selective additions of P(O)-H bonds to carbon-carbon unsaturated compounds, asymmetric hydrophosphorylation reactions, and oxidative/dehydrogenative cross-couplings of P(O)-H bonds with C-H and heteroatom-H bonds. These new reactions provided a series of efficient and atom economic, general and green ways for the preparation of a variety of versatile organophosphorus compounds. Mechanistic aspects related to the catalytic processes are also discussed.

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“…Rhodium-catalyzed addition of HP(O)Ph 2 to terminal alkynes is an efficient process forming linear adducts [29]. Under solvent-free and microwave irradiation conditions, the reaction proceeds efficiently to give the adducts (>75% yields) in a few minutes (1.6 mol% of homogeneous or polymer-bound rhodium catalyst, microwave conditions ¼ 25 W, temp ¼ 120 C) (Scheme 24) [30].…”

Section: Addition Reactions Of Sec-phosphine Oxides With Alkynesmentioning

confidence: 99%

Recent Progress in Transition Metal-Catalyzed Addition Reactions of H–P(O) Compounds with Unsaturated Carbon Linkages

Tanaka

2011

Hydrofunctionalization

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Organophosphorus compounds are playing important roles in our daily life covering a wide range of applications from medicinal use to flame-retardant materials. Although classical synthetic methodologies are still used to synthesize them, the addition reactions of H-P(O) compounds such as H-phosphonates, H-phosphinates, and sec-phosphine oxides have been developed to partially replace the classical methods and are envisioned to be an indispensable tool in the near future. This chapter intends basically to provide recent progress in the field, but not a full scope on the reaction since the same subject was already written by the author in 2004.

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Rhodium-Catalyzed Regio- and Stereoselective Addition of Diphenylphosphine Oxide to Alkynes

Cited by 111 publications

References 25 publications

Diphosphino-Functionalized MCM-41-Immobilized Rhodium Complex: A Highly Efficient and Recyclable Catalyst for the Hydrophosphinylation of Terminal Alkynes

Diphosphino-Functionalized MCM-41-Immobilized Rhodium Complex: A Highly Efficient and Recyclable Catalyst for the Hydrophosphinylation of Terminal Alkynes

Transition Metal-Catalyzed Transformations of P(O)—H Bonds

Recent Progress in Transition Metal-Catalyzed Addition Reactions of H–P(O) Compounds with Unsaturated Carbon Linkages

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