B-alkyl Suzuki-Miyaura cross-coupling reaction

Chemler, S. R., Trauner, D., Danishefsky, S. J. The B-alkyl Suzuki-Miyaura cross-coupling reaction development, mechanistic study, and applications in natural product synthesis. Angewandte Chemie, International Edition 2001,40,4544-4568. 

Anticipating a B-alkyl Suzuki-Miyaura cross-coupling reaction between the Cl-Cl 4 and C15-C24 subunits, alcohol 57 was smoothly converted to vinyl iodide 60 in seven steps, including a Pt02 reduction of the crowded triple bond of intermediate 59, without overreduction. The coupling of the vinyl iodide 60 and C15-C24 subunit was performed by using trialkyl boronate species 61, prepared from alkyl iodide 46, under [Pd(dppf)Cl2] and AsPhs conditions to afford the DDM backbone 62 in 60% yield (Scheme 14). Finally, after carbamate formation and total deprotection, DDM 1 was obtained in 70% yield. The spectroscopic and analytical data of the synthetic samples of as well as their in vitro cytotoxicity levels were in full accord with those of the natural product reported in the literature. 

SCHEME 14 B-alkyl Suzuki-Miyaura cross-coupling reaction between the C1-C14 and C15-C24 subunits 60 and 61. 

Preparation and B-alkyl-Suzuki-Miyaura Cross-coupling Reactions of Functionalized Alkyl Trifluoroborates... 

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