Dramatic rate enhancement of Suzuki diene synthesis. Its application to palytoxin synthesis

Recent applications of the Suzuki–Miyaura cross-coupling reaction in organic synthesis

“…Although TlOH has been used to accelerate the SM crosscoupling reaction at ambient temperature, 223,224 problems associated with its stability and sensitivity promoted a search for alternatives. In this regard, Roush et al have found that TlOEt is more stable and is a less expensive option (Scheme 89).…”

Total Synthesis of (−)-Bafilomycin A1: Application of Diastereoselective Crotylboration and Methyl Ketone Aldol Reactions

“…[28] Hydrolysis of the methyl ester and treatment of the unpurified seco acid with 2,4,6-trichlorobenzoyl chloride and iPr 2 NEt in THF formed the mixed anhydride; the THF was then replaced with toluene, DMAP added, and the reaction mixture heated at reflux for 24 h. This provided macrolactone 15 in 52 % yield. [29] The hindered C7 hydroxyl group of 15 was protected as a TES ether (85 %), then the C19 hydroxyl group was selectively deprotected (90 %) and oxidized to methyl ketone 3 in 98 % yield by using the Dess ± Martin reagent.…”

The B-Alkyl Suzuki-Miyaura Cross-Coupling Reaction: Development, Mechanistic Study, and Applications in Natural Product Synthesis

“…The special rate-enhancing effect of thallium salts in the C(sp 2 )ÀC(sp 2 ) Suzuki reaction was first observed by Kishi and co-workers. [42] Thallium salts have since provided a useful solution for difficult Suzuki couplings in numerous instances. [5, 43±45] Unfortunately, the toxicity of the thallium salts restricts their widespread use.…”