A stereoselective palladium-catalyzed synthesis of amino alkenyl geminal bisphosphonates

Moreau, Pierre; Maffei, Michel

doi:10.1016/j.tetlet.2003.11.031

Cited by 30 publications

(12 citation statements)

References 22 publications

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“…The commercially available dihydroquinine III proved to be the most promising catalyst affording the addition product with moderate enantioselectivity (entry 4). Further screening of temperatures, solvents and concentrations (entries [7][8][9][10][11][12] indicated that toluene is the solvent of choice; moreover, the decrease of both the temperature to À60 8C and the concentration reaction to 0.1 m improved significantly the enantioselectivity to 87 % ee, still maintaining short reaction times.…”

Section: Resultsmentioning

confidence: 99%

“…23-3.93 (m, 8 H), 3.14-3.00 (m, 1 H), 2.98-2.83 (m, 1 H), 2.65 (tt, J = 24.4 Hz, J = 4. 8 Hz, 1 H), 1.35-1.29 ppm (m, 21 H); 13 C NMR (100 MHz, CDCl 3 , 258C): d = 197.4, 167.2, 151.0, 135.6, 130.2, 126.9, 125.2, 123.9, 83.2, 67.3-67.0 (m), 63.0-62.3 (m), 33.4 (t, J = 134.0 Hz), 28.0, 27.4, 16.4-16.0 ppm (m); 31 P NMR (160 MHz, CDCl 3 , 25 8C): d = 23.4, 22.4 ppm; HRMS: m/z: calcd for C 23 H 36 NaO 9 P 2 S: 573.1453, found: 573.1458 [M+Na] + . The ee was determined by HPLC using two Chiralpak AD columns combined in series (hexane/iPrOH 90:10); flow rate 1.0 mL min À1 ; t major = 42.4 min, t minor = 48.5 min (84 % ee).…”

Section: Methodsmentioning

confidence: 99%

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Highly Enantioselective Approach to Geminal Bisphosphonates by Organocatalyzed Michael‐Type Addition of β‐Ketoesters

Capuzzi

Perdicchia

Jørgensen

2007

Chemistry A European J

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A valuable organocatalyzed protocol has been developed for the asymmetric synthesis of bisphosphonate derivatives, a class of pharmaceutically important molecules. Cheap and commercially available dihydroquinine effectively catalyzed conjugate additions of cyclic beta-ketoesters to ethylidenebisphosphonate esters, leading to optically active geminal bisphosphonates, bearing an all-carbon substituted quaternary stereocenter, in high yields and enantioselectivities of up to 99 % ee. Further elaborations of Michael adducts to the corresponding bisphosphonic acids or vinyl phosphonates have also been successfully performed, with conservation of optical purity.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Highly Enantioselective Approach to Geminal Bisphosphonates by Organocatalyzed Michael‐Type Addition of β‐Ketoesters

Capuzzi

Perdicchia

Jørgensen

2007

Chemistry A European J

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“…149 A new and facile synthesis of various 2[alkylamino(diethoxyphosphonyl)methyl] acrylic esters (335) has been developed. 159 An optimized protocol for the preparation of difluoromethylene phosphonate (357) an analogue of b-aspartyl phosphate based on the coupling of protected aspartic acid chloride (358) with difluoromethylphosphonate zinc reagent (359) has been described ( Figure 59). 152 Two alternative routes to methyl-and trifluoromethyl-substituted b-amino and b-hydroxy phosphonates (340) via hydrogenation of vinylphosphonates (341) followed by aldol-type addition of ethylphosphonate to trifluoromethyl substituted imines (342) Olefination of aldehydes with a-silyland a-stannyl-stabilized phosphonate carbanions derived from cyclo-[L-AP4-D-Val] allow a (Z)-selective access to a,b-substituted vinyl phosphonates (343) that have been transformed into enantiomerically pure 4-alkylidene 4PA derivatives (344) (Figure 54).…”

Section: Halogenoalkyl and Halogenocycloalkyl Acidsmentioning

confidence: 99%

Organophosphorus Chemistry

Hall

Bricklebank

Grampel³

et al. 2006

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Organophosphorus compounds are ubiquitous in nature, and due to their innate chemical properties, serve a fundamental role in a number of important fields. Among the more prominent features that elevate their status as a unique and versatile class of compounds, include variable oxidation states, multivalency, asymmetry and metal-binding properties. Their presence in bioactive natural products, endogenous biomolecules, small molecule therapeutic agents and pro-drugs substantiates their role in modern synthetic chemistry and chemical biology. Moreover, their central use as ligands and effectors in asymmetric catalysis, as well as key functional groups for the development of new synthetic methods, has taken the field to new heights. This Thematic Series highlights and details some of the novel methods that are advancing the field of organophosphorus chemistry.The Thematic Series covers topics that range from new synthetic methods and phosphorus-based ligands in asymmetric catalysis to bisphosphonates as promising enzyme inhibitors. More specifically, the Thematic Series spans new methods in C-P bond formation, chiral phosphines in nucleophilic organocatalysis, chiral N-phosphinyl auxiliaries, cyclic phosphonamide reagents in the total synthesis of natural products, phosphinate-containing heterocycles, new routes to phosphinoyl-indoles and phosphinoyl-isocoumarins and new chemistries of H-phosphonates. The Thematic Series also details work on new metathesis-based reactions of vinyl phosphonates and phosphate tethers, novel phosphorus-based ligands in asymmetric catalysis, novel rasta resin-triphenylphosphine oxides and their use as recyclable heterogeneous reagents, the Atherton-Todd reaction, cyclic phosphonium ionic liquids with distinct properties, photo-removable phosphate protecting groups, new methods of C-H functionalization using phosphoryl-related directing groups, the exciting chemistry of substituted phosphanylidenecarbenes and phosphoryl azides, and bisphosphonate ethers as promising inhibitors of geranylgeranyl diphosphate synthase (GGDPS).The articles and reviews capture the emerging potential of organophosphorus compounds and exciting opportunities in the field, and hopefully, will inspire and motivate investigators in the field to investigate new chemistry in this area. Taken collectively, organophosphorus chemistry embodies a broad, vibrant and continual growing scientific area with this Thematic Series highlighting recent advances in the field. We are grateful and indebted to the authors for their hard work and exciting contri-

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“…Transition‐metal‐catalyzed hydroamination of vinylcyclopropanes (VCPs) has also attracted considerable research interests to afford useful amine derivatives. In 2004, Maffei's group reported a Pd‐catalyzed hydroamination of VCPs with amine to afford alkylamine products. Moreover, Togni and co‐workers reported a Au I ‐catalyzed hydroamination of VCPs with sulfonamides to generate useful homoallylic amine derivatives.…”

Section: Introductionmentioning

confidence: 99%

Computational Insights into the Gold‐Catalyzed Ring‐Opening of Methylenecyclopropanes and Vinylcyclopropanes with Sulfonamides

2018

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Computational studies were carried out to investigate the mechanisms of gold‐catalyzed ring‐opening of methylenecyclopropanes (MCPs) and vinylcyclopropanes (VCPs), respectively, with sulfonamides to afford homoallylic amine intermediates, which would subsequently produce pyrrolidine derivatives. The detailed activation modes of MCPs mediated by the AuI catalyst were comprehensively explored. Computational results suggested that the activation of MCP by the AuI catalyst was less feasible. Instead, the AuI catalyst mediated activation of sulfonamides could result in the increased acidity of the N−H bond, which is ready to undergo intermolecular proton transfer to the C=C moiety of MCP to form a cyclopropylcarbinyl cation intermediate. Subsequently, the nucleophilic attack of the formed amido group to the three‐membered ring moiety of the yielded cyclopropylcarbinyl cation intermediate in an SN2 manner could follow to afford the ring‐opening homoallylic sulfonamide. In addition, computational studies indicated that such mechanistic pathway could also apply to the VCPs involved hydroamination with sulfonamides. The mechanism of triflic acid catalyzed hydroamination of MCPs and VCPs with sulfonamides also proceeds via the cyclopropylcarbinyl cation intermediates formed by the protonation of the alkene moiety of MCPs and VCPs, respectively. The ineffectiveness of amines as aminating reagents in the AuI‐catalyzed hydroamination of MCPs and VCPs was discussed.

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A stereoselective palladium-catalyzed synthesis of amino alkenyl geminal bisphosphonates

Cited by 30 publications

References 22 publications

Highly Enantioselective Approach to Geminal Bisphosphonates by Organocatalyzed Michael‐Type Addition of β‐Ketoesters

Highly Enantioselective Approach to Geminal Bisphosphonates by Organocatalyzed Michael‐Type Addition of β‐Ketoesters

Organophosphorus Chemistry

Computational Insights into the Gold‐Catalyzed Ring‐Opening of Methylenecyclopropanes and Vinylcyclopropanes with Sulfonamides

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