High chemoselectivity in the phenol synthesis

• Matthias Rudolph,
• Melissa Q. McCreery,
• Wolfgang Frey and
• A. Stephen K. Hashmi

Beilstein J. Org. Chem. 2011, 7, 794–801, doi:10.3762/bjoc.7.90

• ][24][25]. Moreover, interesting new pathways were opened when ynamides and alkynyl ether substrates were employed: Here A is also a possible intermediate along these pathways [25]. Since direct experimental evidence existed only for C and D, we intended to intercept the postulated carbenoid

Recent advances in carbocupration of α-heterosubstituted alkynes

• Ahmad Basheer and
• Ilan Marek

Beilstein J. Org. Chem. 2010, 6, No. 77, doi:10.3762/bjoc.6.77

• change the stereochemical outcome of the reaction. Representative examples are given in this mini-review. Keywords: alkynes; carbocupration; enamides; regioselectivity; stereoselectivity; syn-addition; vinylcopper; ynamides; ynol ether; Review The addition of a carbon-metal bond of an organometallic

• the charge distribution in the alkyne (electron donating nitrogen atom induces polarization) [11][12][13]. To obtain the opposite regioisomer for nitrogen-substituted alkynes (linear isomer), it is essential to overcome the effect of the electron-donating heteroatom. Therefore, ynamides 17

• adduct 29. However, the reaction was not completely stereoselective (Scheme 13) [25]. Although not a copper-mediated transformation, the rhodium-catalyzed carbozincation of ynamides should be noted since the regioselectivities were, in general, high (>19:1), though in some cases somewhat diminished with