, 400 MHz, CDCl3) ? (ppm) 13.60 (bs, 1H, NH), 7.44-7.17 (m, 5H, H-6, H-7, vol.1
C-5), 100.6 MHz, CDCl3) ? (ppm) 205.0 (C-2), vol.144, pp.19-20 ,
, IR (Neat) ?max (cm -1 ) 3449 (??OH), vol.3029, p.566, 1017.
, HRMS m/z calcd for C23H40N2O2Si
, After 1 h stirring at the same temperature, the reaction mixture was cooled to -78 °C and a solution of aldehyde (1 equiv) in anhydrous Et2O (4.8 mL/mmol of aldehyde) was added dropwise. After an additional 1 h or 5 h stirring at -78 °C, the reaction mixture was quenched with saturated aqueous NH4Cl and slowly warmed to rt. The aqueous layer was extracted with Et2O (x3). The combined organic layer was washed with brine, dried (Na2SO4), filtered and the filtrate was concentrated under reduced pressure
, to 5:5) to afford the corresponding hydrazones 80 and 81
Methyl-side" aldolisation on ?-triisopropylsilyl-?-diazoacetone 2 via boron enolates 1) With chlorodicyclohexylborane ,
, This solid was dissolved in Et2O (4 mL), and a buffered aqueous solution (pH = 7; 0.3 mL) and hydrogen peroxide (5 µL) were added. The mixture was stirred 3 h between 0 °C and 5 °C. The organic layer was washed with brine (4 mL), dried (MgSO4), filtered and the filtrate was concentrated under reduced pressure. The residue was chromatographed (silica gel neutralized with 2% of NEt3; petroleum ether/ethyl acetate 10:0 to 5:5) to afford the corresponding diazoaldol 3a as a yellow solid. (114 mg; 83% yield). The aldol 3a was, anhydrous Et2O
, With (-)-B-chlorodiisopinocampheylborane
, To a stirred solution of ?-triisopropylsilyl-?-diazoacetone 2 (95 mg; 0.42 mmol) in anhydrous Et2O (3 mL) at -78 °C were added slowly triethylamine (90 µL; 0.63 mmol) and then
, 5 h stirring, a solution of benzaldehyde (51 µL; 0.50 mmol) in anhydrous Et2O (1mL) was added dropwise
, Hydrogen peroxide (30 µL) was added and the mixture was stirred for 10 min between 0 °C and 5 °C. The organic layer was washed with brine (4 mL), dried (MgSO4), filtered and the filtrate was concentrated under reduced pressure. The residue was chromatographed (silica gel neutralized with 2% of NEt3; petroleum ether/ethyl acetate 10:0 to 5:5) to afford the corresponding diazoaldol 3a as a yellow solid (116 mg; 84% yield). The final product was contaminated with traces of diisopinocampheol. The aldol 3a was, After an additional 5 h stirring at -78 °C, the reaction mixture was quenched with a buffered solution
, Université d'Angers, TIPS-Diazoacetone: new building-block for the convergent elaboration of functionalized carbon chains, Poster pour les JED (Journée de l'Ecole Docotrale), 2017.
, TIPS-Diazoacetone: new building-block for the convergent elaboration of functionalized carbon chains, Sigrid Gavelle, Gilles Dujardin, Catherine Gaulon-Nourry, vol.29, 2018.
, TIPS-Diazoacetone: new building-block for the convergent elaboration of functionalized carbon chains, * Communications à des colloques/congrès avec actes SCF-BPL-2017, 2017.
TIPS-Diazoacetone: new building-block for the convergent elaboration of functionalized carbon chains, Catherine Gaulon-Nourry, pp.12-17, 2019. ,
, Nuit européenne des chercheurs, 28 septembre 2017, Le Mans, Vulgarisation des thématiques de recherche de l'équipe MSO
, Expériences de chimie in the TBAF-induced aldol-type addition of ?-trialkylsilyl-?-diazoacetones: TIPS versus, vol.20, pp.595-600, 2017.
Imen Abid Walha, Stéphane Bidou, Andreas Kirschning, Gilles Dujardin and Catherine Gaulon-Nourry* ,
, Soumission prévue dans le journal Synthesis, article de type Practical Synthetic Procedures
,
, Soumission prévue dans le journal : The Journal of Organic Chemistry
, Tetrahedron, vol.68, pp.9652-9657, 2012.
, J. Org. Chem, vol.80, issue.20, pp.9980-9988, 2015.
, Tetrahedron Lett, vol.38, pp.1415-1419, 1997.
, Org. Lett, vol.12, pp.796-799, 2010.
, Org. Biomol. Chem, vol.78, pp.7159-7166, 2013.
, Eur. J. Org. Chem, vol.18, issue.19, pp.3979-3986, 2015.
, Angew. Chem. Int. Ed, vol.44, pp.2773-2776, 1913.
, J. Am. Chem. Soc, vol.96, pp.7503-7509, 1974.
, Tetrahedron: Asymmetry, vol.7, pp.2093-2096, 2005.
, Org. Chem, vol.73, pp.1971-1974, 2008.
, Tetrahedron Lett, vol.53, pp.5087-5090, 1997.
, J. Org. Chem, vol.62, pp.194-198, 1997.
, J. Org. Chem, vol.54, pp.7983-7987, 1998.
, J. Am. Chem. Soc, vol.66, pp.13121-13126, 2001.
, Tetrahedron, vol.65, pp.5904-5907, 2009.
, J. Org. Chem, vol.40, pp.3521-3528, 1975.
, J. Org. Chem, vol.76, issue.18, pp.9464-9470, 2011.
, J. Org. Chem, vol.62, pp.1934-1939, 1997.
, J. Chem. Soc. Perkin Trans. 1, vol.20, pp.2566-2569, 1979.
, Tetrahedron, vol.45, pp.5517-5530, 1989.
,
, , vol.21, pp.2988-2992, 2019.
, Travaux de thèse non publiés d'Anthony Lancou sur la TBS-diazoacétone réalisés à l'université du Mans
,
, J. Organomet. Chem, vol.142, pp.155-164, 1977.
, Chem. Ber, vol.120, pp.635-641, 1987.
, J. Agric. Food. Chem, vol.24, pp.2849-2855, 1983.
, Justus Liebigs Ann. Chem, vol.676, pp.101-109, 1964.
, Org. Process Res. Dev, vol.6, pp.884-892, 2002.
, J. Org. Chem, vol.33, pp.3610-3618, 1968.
, Synthesis, vol.16, pp.2549-2552, 2011.
, Synth. Commun, vol.17, issue.14, pp.1709-1716, 1987.
, J. Am. Chem. Soc, vol.135, pp.17990-17998, 2013.
, Synthesis, vol.17, pp.2871-2874, 2005.
, Synlett, vol.18, pp.2943-2944, 2009.
, Tetrahedron Lett, vol.45, pp.1390-1401, 2004.
, Chem. Commun, vol.55, pp.4284-4290, 2019.
, , 2016.
e-EROS encyclopedia of reagents for organic synthesis, pp.1-2, 2001. ,
, Synthesis, vol.5, pp.1025-1030, 2008.
, Synthesis, vol.24, pp.4266-4268, 2006.
, Org. Synth, vol.85, pp.278-286, 2008.
, Synthesis, vol.5, pp.723-730, 2011.
, Tetrahedron, vol.48, pp.4733-4748, 1992.
, J. Org. Chem, vol.55, pp.2304-2306, 1990.
, Organic Process Research & Development, vol.12, pp.1285-1286, 2008.
, Angew. Chem. Int. Ed. Engl, vol.25, pp.478-479, 1986.
, Review sur les dangers associés à la manipulation et l'utilisation de NaN3 en synthèse : Archibald, T
, Soumission prévue dans le journal Synthesis, article de type Practical Synthetic Procedures
, Chem. Eur. J, vol.9, pp.5708-5723, 2003.
, Chem. Eur. J, vol.24, pp.10571-10583, 2018.
, Org. Biomol. Chem, vol.14, pp.3423-3431, 2016.
, Eur. J. Org. Chem, pp.6533-6539, 2017.
, Org. Lett, vol.13, pp.320-323, 2011.
, J. Org. Chem, vol.31, pp.3880-3882, 1966.
, Beilstein J. Org. Chem, vol.1, pp.1-6, 2005.
, , vol.20, pp.595-600, 2017.
, TES-diazoacétone 35 synthétisée par Frédéric Legros, technicien CNRS, IMMM
, , 2015.
, Analyses DRX réalisées par les Dr
, Angew. Chem. Int. Ed, vol.129, pp.2622-2632, 1989.
, The chemisty of organolithium compounds, vol.57, p.549, 1992.
, Angew. Chem. Int. Ed, vol.6, pp.4417-4420, 1960.
, J. Chem. Soc. Dalton Trans, pp.501-508, 1987.
, Tetrahedron Lett, vol.53, pp.6489-6491, 2012.
, Org. Synth, p.146, 1993.
, Modélisation moléculaire et diagramme d'enthalpie libre réalisé par le Pr, Arnaud Martel
, Calculs réalisés au niveau B3LYP/6-31+G(d) par le Pr, Arnaud Martel
, Aldéhydes précurseurs des diazoaldols 3o à 3q synthétisés par Frédéric Legros, technicien CNRS, et
, , 2017.
, J. Am. Chem. Soc, vol.136, pp.1082-1089, 2014.
thèse portant sur l' « Aldolisation des ?-trialkylsilyl-?-diazoacétones induite par l'ion fluorure ,
, J. Org. Chem, vol.54, pp.1570-1576, 1989.
, Chem. Rec, vol.17, pp.622-639, 2017.
, J. Org. Chem, vol.82, pp.4949-4957, 2017.
, J. Am. Chem. Soc, vol.139, pp.527-533, 2017.
, J. Org. Chem, vol.63, pp.8380-8389, 1998.
, Tetrahedron, vol.64, pp.915-925, 2008.
, Chem. Commun, pp.1199-1120, 1999.
, Beilstein J. Org. Chem, vol.1, pp.5503-5512, 2005.
, Angew. Chem. Int. Ed. Engl, vol.30, pp.10053-10072, 1991.
, Eur. J. Org. Chem, pp.2633-2643, 1999.
, Eur. J. Org. Chem, vol.16, pp.1894-1903, 2003.
, Angew. Chem. Int. Ed, vol.39, pp.2288-2290, 2000.
, , pp.461-464, 2005.
, Tetrahedron: Asymmetry, vol.39, pp.1503-1510, 1998.
, Tetrahedron: Asymmetry, vol.18, pp.1795-1798, 2007.
, Adv. Synth. Catal, vol.357, pp.317-322, 2013.
, Synth. Commun, vol.48, pp.2477-2481, 1975.
, J. C. S. Chem. Comm, pp.537-538, 1975.
, Org. Biomol. Chem, vol.103, pp.4745-4747, 1981.
, Organometallics, vol.3, pp.1583-1585, 1984.
, Angew. Chem. Int. Ed, vol.55, pp.218-222, 2016.
, Eur. J. Org. Chem, vol.2012, pp.6959-6966
, J. Am. Chem. Soc, vol.80, pp.770-773, 2013.
, J. Org. Chem, vol.51, pp.986-992, 1986.
, J. Am. Chem. Soc, vol.140, pp.17439-17443, 2018.
, Travaux d'extension « diazo-side » sur la TIPS-diazoacétone 2 réalisés conjointement avec Imen Abid Walha lors de sa thèse, Les premiers essais avaient été réalisés au cours de mon stage de M1 en 2015 à Le Mans Université
, Tetrahedron, vol.53, pp.16299-16312, 1997.
, Org. Biomol. Chem, vol.108, pp.1106-1109, 1986.
, Prudent Practices for Disposal of Chemicals From Laboratories, pp.87-88, 1991.
, J. Org. Chem, vol.43, pp.188-196, 1978.
, J. Organomet. Chem, vol.448, pp.1-3, 1993.
, J. Org. Chem, vol.64, pp.3755-3756, 1999.
, J. Organomet. Chem, vol.542, pp.281-283, 1997.
, Org. Lett, vol.21, pp.2988-2992, 2019.
, J. Am. Chem. Soc, vol.136, pp.1082-1089, 2014.
, J. Am. Chem. Soc, vol.132, pp.3258-3259, 2010.
, Org. Lett, vol.9, issue.16, pp.3129-3132, 2007.
, Tetrahedron, vol.53, pp.16299-16312, 1997.