Synthesis and Applications - The Anderson Research Group

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Alkynes - Silylformylation Terminal and Internal Alkynes Silylformylation of tethered dimethylsilyl ether-alkynes by Rh and Rh-Co complexes proceeds with opposite regioselectivity to the intermolecular reaction, forming exo-oxasilacycles exclusively. Internal alkynes and cyclic systems are tolerated, affording tetrasubstituted and bicyclic vinyl silanes respectively with complete regio- and stereoselectivity. Oxasilacyclobutanes and heptanes could not be prepared by this method. Ojima, I.; Vidal, E.; Tzamarioudaki, M.; Matsuda, I. J. Am. Chem. Soc. 1995, 117, 6797-6798. Si O CHO C 4 H 9 unstable to purification O Si CHO formed in trace amounts
Alkynes - (Carbonylative) Silylcarbocyclisation Terminal and Internal Alkynes Silylcarbocyclisation (SiCaC) of 1,6-enynes Ojima and co-workers reported a versatile hydrosilylation-carbocyclisation with Rh catalysts. • Esters, ethers, sulfonamides and amines; (free hydroxyls react in lower yields) • Aryl and alkoxysilanes - HSiMe 2 Ph,HSiMe(OEt) 2 ; • Internal alkynes reacted in excellent yields (83-95%). Carbonylative Silylcarbocyclisation (CO-SiCaC) of 1,6-enynes High CO concentration, elevated temperature and an external trapping ligand promoted the formation of silylformylated product. Denmark and co-workers have utilised CO-SiCaC to prepare the pyrrolidine fragment of isodomoic acids G and H. • Disubstituted alkenes and dienes; • 1,7-enynes; • Bulky silanes – HSiMe 2 (t-Bu) underwent no or poor conversion. Ojima, I.; Vu. A.T.; Lee, S.-Y.; McCullagh, J.V.; Moralee, A.C.; Fujiwara, M.; Hoang, T.H. J. Am. Chem. Soc. 2002, 124, 9164-9174. Isodomoic acids G/H: Denmark, S.E.; Liu, J.H.-C.; Muhuhi, J.M. J. Am. Chem. Soc. 2009, 131, 14188-14189.
Page 1 and 2: Alkenyl Silanes - Synthesis and App
Page 3 and 4: Introduction SiR' 3 R Advantages of
Page 5 and 6: Alkynes - Hydrosilylation Terminal
Page 7 and 8: Alkynes - Hydrosilylation Terminal
Page 9: Alkynes - Hydrosilylation Internal
Page 13 and 14: Silyl Alkynes Preparation of Silyl
Page 15 and 16: Silyl Alkynes - Hydrometallation Hy
Page 17 and 18: Silyl Alkynes - Carbometallation Al
Page 19 and 20: Synthesis of Alkenyl Silanes Alkyne
Page 21 and 22: Terminal Vinyl Silanes - Heck Coupl
Page 23 and 24: Synthesis of Alkenyl Silanes Alkyne
Page 25 and 26: Aldehyes - Peterson-Type Olefinatio
Page 27 and 28: Carbon-Oxygen Bond Formations Epoxi
Page 29 and 30: Carbon-Oxygen Bond Formations Tamao
Page 31 and 32: Applications of Alkenyl Silanes Car
Page 33 and 34: Carbon-Carbon Bond Formations Hiyam
Page 35 and 36: Carbon-Carbon Bond Formations Hiyam
Page 37 and 38: Carbon-Carbon Bond Formations Other
Page 39 and 40: Carbon-Carbon Bond Formations Cu(I)
Page 41: Thank you!

Synthesis and Applications - The Anderson Research Group

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