Why Are Organotin Hydride Reductions of Organic Halides So Frequently Retarded? Kinetic Studies, Analyses, and a Few Remedies

• Published in: Journal of organic chemistry Vol. 80; no. 3; pp. 1321 - 1331
• Main Authors: Ingold, K. U, Bowry, Vincent W
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 06.02.2015
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo502710a

Kinetic data for reduction of organic halides (RX) by tri-n-butylstannane (SnH) reveal a serious flaw in the current view of the kinetic radical chain: the tacit but unproven assumption that the speed of reaction is determined by the slowest propagation step. Our results show this is rarely true for reductive chains and that the observed rate is in fact controlled by unseen side-reactions of propagating R• and Sn • radicals with the solvent (notably, benzene!) or solvent impurities (e.g., trace benzophenone dryness indicator in THF) or, crucially, with allylic-CH and conjugated unsaturated groups in substrates and products. Most R• and/or Sn • radicals are therefore converted into relatively inert delocalized species A • and/or B • that inhibit the chain. Retardation in the degraded chain is given by a simple sum of terms, each being the ratio of the chain-transfer rate divided by the rate of chain-return. The model kinetic equation is linear and easy to ratify, interpret, and apply: to calculate retarding rate constants, optimize reaction conditions, and identify additives or “remedies” that repair the chain and accelerate reaction. The present work is thus expected to have a helpful impact on the practice and design of SnH radical chain based (and related) syntheses.