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The synthesis of bench-stable α,α-bis(trimethylsilyl)toluenes and tris(trimethylsilyl)methane is described and their use in stereoselective Peterson olefinations has been achieved with a wide substrate scope. Product stereoselectivity was poor with carbonyl electrophiles (E/Z ∼1:1 to 4:1) though this was significantly improved by employing the corresponding substituted N-benzylideneaniline (up to 99:1) as an alternative electrophile. The olefination byproduct was identified as N,N-bis(trimethylsilyl)aniline and could be easily separated from product by aqueous acid extraction. Evidence for an autocatalytic cycle has been obtained., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The synthesis of bench-stable α,α-bis(trimethylsilyl)toluenes and tris(trimethylsilyl)methane is described and their use in stereoselective Peterson olefinations has been achieved with a wide substrate scope. Product stereoselectivity was poor with carbonyl electrophiles ( E/ Z ∼1:1 to 4:1) though this was significantly improved by employing the corresponding substituted N-benzylideneaniline (up to 99:1) as an alternative electrophile. The olefination byproduct was identified as N, N-bis(trimethylsilyl)aniline and could be easily separated from product by aqueous acid extraction. Evidence for an autocatalytic cycle has been obtained. [ABSTRACT FROM AUTHOR]

A new general two-step approach for the synthesis of bench-stable α,α-bis(trimethylsilyl)toluenes and tris(trimethylsilane) is developed. [ABSTRACT FROM AUTHOR]

Peterson olefination as represented by the building facade is one of the historic yet still essential building blocks of synthetic chemistry. In their Communication on page 8737 ff., D. O'Shea et al. report on the first stereoselective aza ‐ Peterson reaction utilising bench stable geminal bis ‐ silane reagents with imine substrates. These advances have allowed several long ‐ standing limitations for this double bond forming reaction to be overcome. The facade itself is the entrance into the original building of the Royal College of Surgeons in Ireland which has housed the chemistry department since its foundation in 1828. [ABSTRACT FROM AUTHOR]