Organoboranes. 52. The successful ring enlargement of boracyclanes via sequential one-carbon homologation: The first synthesis of boracyclanes in the strained medium-ring range

Previous attempts to synthesize boracyclanes in the medium-ring range (9-, 10-, 11-, and 12-ring members) via cyclic hydroboration of α,ω-dienes have failed. However, their synthesis via the sequential one-carbon homologation of B-methoxyboracyclanes has been achieved utilizing the successive reaction of B-methoxyboracyclanes with in situ generated (chloromethyl)lithium (LiCH₂Cl): MeOB(CH₂)₅ → MeOB(CH₂)₆ → MeOB(CH₂)₇ → MeOB(CH₂)₈ → MeOB(CH₂)₉ → MeOB(CH₂)₁₀ → MeOB(CH₂)₁₁. The yields achieved are in the range of 75–85%. In each case the products are identified by conversion via the DCME reaction into the known cycloalkanones. This development provides the first entry into boracyclanes of the strained medium ring range.