Convenient Method for the Reduction of the Double-Bond of Cyclic Vinylphosphine Oxides Using Borane

Keglevich, György; Fekete, Melinda; Chuluunbaatar, Tungalag; Dobó, András; Bocskei, Z.; Tőke, L.

doi:10.1080/00397910008087043

Cited by 13 publications

(16 citation statements)

References 8 publications

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“…The hydroxyl groups in 2a-2g and 2j were oxidized using IBX [46], and then the conjugated double bond was reduced using the borane dimethyl sulfide complex (Scheme 5; Table 2). Boranes have already been used in combination with silanes as reducing agents for some particular type of double bonds [47][48][49][50][51]; however, the only example where the borane dimethyl sulfide complex was used to reduce electronically poor double bonds was reported some years ago for cyclic vinylphosphine oxides or dihydrophosphole oxides [52][53][54]. Thus, the usage of the borane dimethyl sulfide complex to reduce the double bonds of oxidized MBH adducts represents a new and chemoselective methodology to reduce this type of system.…”

Section: Resultsmentioning

confidence: 99%

Morita–Baylis–Hillman adducts as building blocks of heterocycles: a simple approach to 4-substituted pyrazolones, and mechanism investigation via ESI–MS(/MS)

et al. 2015

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We describe herein an efficient approach for the preparation of 4-substituted 2,3-dihydro-1H-pyrazol-3-ones starting from Morita-Baylis-Hillman adducts. These heterocycles were obtained in two or three steps as single isomers with moderate to good overall yields. One efficient and alternative methodology for the synthesis of a-methylb-ketoesters is also reported (up to 91 % yield). Additionally, the mechanism of formation of pyrazolones was investigated employing ESI-MS/MS reaction monitoring. Graphical abstract

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Section: Resultsmentioning

confidence: 99%

Morita–Baylis–Hillman adducts as building blocks of heterocycles: a simple approach to 4-substituted pyrazolones, and mechanism investigation via ESI–MS(/MS)

et al. 2015

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“…Three kinds of P-heterocycles having considerable ring strain were found to be especially suitable starting materials to undergo the above change: tetrahydrophospole oxides 5a and 36, 3-phosphabicyclo[3.1.0]hexane oxide 38, and phosphole oxide dimers 40, 42, and 44 (Table 2) [1,15,16]. The corresponding phosphine boranes (35, 37, 39, 41, 43, and 45, respectively,) were obtained in 47-92% yields.…”

Section: One-pot Transformation Of the Phosphine Oxide Function Of P-mentioning

confidence: 96%

“…It was, however, more suitable to use 1,2,3,4-tetrahydrophosphinine oxide 7 as the starting material in the synthesis of hexahydrophosphinine oxide 8 (entry 4). As exemplified in Scheme 2, the selective re- duction could also be extended to alicyclic vinyl phosphine oxides [1]. As a matter of fact, the selective saturation was first observed during the preparation of unsaturated phosphine boranes from the corresponding phosphines and BMS as described by Mathey [3], and later by us [4].…”

Section: Introductionmentioning

confidence: 97%

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Selective reductions in the sphere of organophosphorus compounds

Keglevich

Gaumont

Denis

2001

Heteroatom Chemistry

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“…The remaining , -doublebond of 1,2,3,4-tetrahydrophosphinine oxide 46 could also be reduced by a second portion of borane to afford 4-dichloromethylene-hexahydrophosphinine oxide 47. Both 46 and 47 were obtained as a mixture of diastereomers (Scheme 22) [31].…”

Section: Saturated Derivatives From 12-dihydrophosphinine Oxidesmentioning

confidence: 99%

6-Membered P-Heterocycles: 1,2-Dihydro-, 1,2,3,6-Tetrahydro- and 1,2,3,4,5,6-Hexahydrophosphinine 1-Oxides

Keglevich

2006

COC

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The members of a logically built P-heterocyclic family are discussed systematically to show a dynamically developing discipline of organophosphorus chemistry. Dichlorocyclopropanation of 2,5-dihydro-1H-phosphole oxides led to 3-phosphabicyclo[3.1.0]hexane 3-oxides that were useful intermediates for the synthesis of ring expanded products, such as 1,2-dihydrophosphinine oxides and 3-alkoxy-1,2,3,6-tetrahydrophosphinine oxides. Catalytic hydrogenation of 1,2-dihydrophosphinine oxides gave 1,2,3,4,5,6-hexahydrophosphinine oxides. Selective reduction of the , -doublebond of 1,2-dihydrophosphinine oxides via hydroboration led to 1,2,3,6-tetrahydrophosphinine oxides. Michael addition of >P(O)H species to the electron-poor double-bond of 1,2-dihydrophosphinine oxides afforded 1,2,3,6-tetrahydrophosphinine oxides with exocyclic P-function in position 3. Hydrogenation of these P-heterocycles led to the corresponding hexahydrophosphinine oxides. Stereostructure and conformation of the tetra-and hexahydrophosphinine oxides were elucidated by stereospecific NMR couplings and/or quantum chemical calculations. After deoxygenation, some of the above P-heterocycles were suitable P-ligands in transition metal complexes. The 1,2-dihydrophosphinine oxides were also useful in the synthesis of aromatic phosphinines, phosphepine derivatives and phosphabicyclo[2.2.2]octene oxides, as well as hetrocyclic -oxophosphoranes.

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Convenient Method for the Reduction of the Double-Bond of Cyclic Vinylphosphine Oxides Using Borane

Cited by 13 publications

References 8 publications

Morita–Baylis–Hillman adducts as building blocks of heterocycles: a simple approach to 4-substituted pyrazolones, and mechanism investigation via ESI–MS(/MS)

Morita–Baylis–Hillman adducts as building blocks of heterocycles: a simple approach to 4-substituted pyrazolones, and mechanism investigation via ESI–MS(/MS)

Selective reductions in the sphere of organophosphorus compounds

6-Membered P-Heterocycles: 1,2-Dihydro-, 1,2,3,6-Tetrahydro- and 1,2,3,4,5,6-Hexahydrophosphinine 1-Oxides

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