Novel balanced out organoboron accomplices for the Suzuki-Miyaura cross-coupling response .


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Novel stabilized organoboron partners for the Suzuki-Miyaura cross-coupling reaction. By Olga Dykhno. 1. Metal- Catalyzed Cross- Coupling Reactions . 2nd ed. Ed. De Meijere, A.; Diederich, F. Wiley- VCH. Weinheim, 2004. .
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Novel settled organoboron accomplices for the Suzuki-Miyaura cross-coupling response By Olga Dykhno

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1 Metal-Catalyzed Cross-Coupling Reactions . second ed. Ed. De Meijere, A.; Diederich, F. Wiley-VCH. Weinheim, 2004.

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Miyaura, N.; Suzuki, A. J. Chem. Soc., Chem. Commun. 1979 , 866 - 867. Miyaura, N.; Yanagi, T.; Suzuki, A. Synth. Commun . 1981 , 11 , 513 - 519. 2

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Walker, S.D.; Barber, T.W.; Martinelli, J.R.; Buchwald, S.L. Angew. Chem. Int. Ed. 2004 , 43, 1871-1876 – 867; Bhayanna, B.; Fors, B.P.;Buchwald, S.L. Organization. Lett ., 2009 , 11 , 3954-3957. 3

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4 Nicolaou, K.C.; Bulger, P.G.; Sarlah, D. Angew. Chem. Int. Ed . 2005 , 44 , 4442-4489.

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Boronic acids . Ed. Lobby, D.G, Wiley-VCH. Weinheim, 2005; Molander, G.A.; Canturk, B. Angew. Chem. Int. Ed., 2009 , 48 , 9240-9262.; 5

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Boronic acids are trivalent boron-containing natural mixes Mild natural Lewis acids Low lethality and corrupts into ecologically well disposed boric corrosive Products of second oxidation of boranes Formation of boronic esters – loses hydrogen bond benefactor abilities Boronic esters are less polar, simpler to handle Boronic esters are non molecule prudent 7 Boronic acids . Ed. Lobby, D.G, Wiley-VCH. Weinheim, 2005.

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Limitations Boronic acids are not monomeric species, but instead exist as dimeric and cyclic trimeric anhydrides. Because of simple protodeboronation, overabundance (20-half) of boronic corrosive is required. Affectability to reagents generally utilized as a part of natural combination 8 Boronic acids . Ed. Lobby, D.G, Wiley-VCH. Weinheim, 2005.

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First report of advantageous union of organotrifluoroborates utilizing boronic corrosive and subordinates utilizing KHF 2 First to use organotrifluoroborates in coupling responses with arenediazonium tetrafluoroborates. Vedejs, E.;Chapman, R.W.; Fields, S.C.; Lin, S.; Schrimpf, M.R. J. Organization. Chem. 1995 , 60 , 3020-3027; Darses, S.; Genet, J.P.; Brayer, J.L.; Demoute, J.P. Tetrahedron Lett. 1997 , 38 , 4393-4396. 9

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Advantages Monomeric, crystalline intensifies that are effortlessly taken care of and uncertainly stable to dampness and air. BF 3 K moiety is good with touchy useful gatherings Tolerant to response conditions. 10 Darses,S.; Michaud, G.; Genet, J.- P . Eur.J.Org.Chem., 1999 , 1875-1883.

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Molander, G.A.; Cooper, D.J. J. Organization. Chem. 2007 , 72 , 3558-3560; Molander, G.A.; Petrillo, D.E. J. Am. Chem. Soc . 2006 , 128 , 9634-9635. 11

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Potassium heteroaryl trifluoroborates with aryl chlorides. Coupling of vinyl trifluoroborates with aryl triflates Electron poor aryl bromide with electron-insufficient aryltrifluoroborates. Molander, G.A.; Biolatto, B. J. Organization. Chem . 2003 , 68 , 4302-4306; Molander, G. A.;Rivero, M.R. Organization. Lett. 2002 , 4 , 107-111; Molander, G.A.; Canturk, B. Organization .Lett. 2008 , 10, 2135-2138 ; Barber, T.E.; Buckwald, S.L. Org.Lett . 2004 , 6 , 2649-2652. 12

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13 Molander, G.A.; Canturk, B. Organization .Lett. 2008 , 10, 2135-2138 .

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14 Molander, G.A.; Canturk, B. Organization .Lett. 2008 , 10, 2135-2138 .

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15 Molander, G.A.; Sandrock, D.L. J. Am. Chem. Soc . 2008 , 130 ,15792-15793.

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16 Molander, G.A.; Sandrock, D.L. J. Am. Chem. Soc . 2008 , 130 ,15792-15793.

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Iterative Cross-Coupling criteria Building squares are promptly accessible and reasonable Coupling and Protection/deprotection are high yielding, practical gathering tolerant and don\'t deliver poisonous by-items Handling, division, and filtration are effortless 18 Madabe, K.; Ishikawa, S. Chem.Comm 2008 , 3829-3838.

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Coupling of arylboronic corrosive A with haloboronic corrosive C – no sought item. Development of blend of oligoarenes Coupling of arylboronic corrosive A with "veiled" haloboronic corrosive C\' - coveted item. 19 Noguchi, H.; Hojo, Kosho.; Suginome, M. J. Am. Chem. Soc . 2007 , 129 ,758-759.

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Masking Group Requirements Easy establishment High security amid coupling and disconnection prepare Easy unmasking 20 Noguchi, H.; Hojo, Kosho.; Suginome, M. J. Am. Chem. Soc . 2007 , 129 ,758-759.

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21 Noguchi, H.; Hojo, Kosho.; Suginome, M. J. Am. Chem. Soc . 2007 , 129 ,758-759.

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22 Noguchi, H.; Shioda, T.; Chou, C.- M.;Suginome, M. Org.Lett . 2008 , 10 , 377-380..

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23 Noguchi, H.; Shioda, T.; Chou, C.- M.;Suginome, M. Org.Lett . 2008 , 10 , 377-380..

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Boron veiling methodology 25 Gillis, E.P.; Burke, M.D. J. Am. Chem. Soc . 2007 , 129 , 6716-6717.

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26 Gillis, E.P.; Burke, M.D. J. Am. Chem. Soc . 2007 , 129 , 6716-6717.

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27 Gillis, E.P.; Burke, M.D. J. Am. Chem. Soc . 2007 , 129 , 6716-6717.

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MIDA boronate useful gathering is steady to an extensive variety of normal engineered reagents Further elaboration or increment in atomic multifaceted nature is conceivable with MIDA boronates 28 Gillis, E.P.; Burke, M.D. J. Am. Chem. Soc . 2008 , 130 , 14084-14085.

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29 Gillis, E.P.; Burke, M.D. J. Am. Chem. Soc . 2008 , 130 , 14084-14085.

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30 Knapp, D.M.; Gillis, E.P.; Burke, M.D. J. Am. Chem. Soc . 2009 , 131 , 6961-6963.

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31 Knapp, D.M.; Gillis, E.P.; Burke, M.D. J. Am. Chem. Soc . 2009 , 131 , 6961-6963.

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33 Gillis, E.P.; Burke, M.D. J. Am. Chem. Soc . 2007 , 129 , 6716-6717.

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34 Gillis, E.P.; Burke, M.D. J. Am. Chem. Soc . 2007 , 129 , 6716-6717.

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Solubility issues are available Unmasking requires brutal conditions Functional gathering resistance was not represented Expensive securing bunch Loss of molecule economy 35

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Additional practice talk participants Teresa Beary J.P. Gerdt Brad Ryland Nicky Stephenson Adam Weinstein Professor Tehshik Yoon Kat Myhre Steve Burke Yoon Group Kevin Williamson Tamas Benkovics Juana Du Elliot Farney Michael Ischay Shishi Lin Dr. Zic Lu Dr. David Michaelis Dr. Katie Partridge Jon Parrish Laura Ruiz Espelt Liz Tyson 36

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