Bridged Polycyclic Compounds. XIV. Free-Radical Addition of p-Toluene-sulfonyl Chloride to Some Norbornenes¹

Free-radical additions to olefins in the presence of redox systems

“…This stereoselectivity was attributed to coordination of the unprotonated amino group with the ferric salt which is mainly responsible for the chlorine atom transfer13 As (eq 17). The protonated amino radical o €1 80% + Fe (17) would not be expected to form such a complex, and therefore a less stereospecific reaction would occur.…”

(E)-1-(Phenylsulfonyl)-4-(trimethylsilyl)-1-butene: An Advantageous Synthetic Equivalent for the 1-(1,3-Butadienyl) Anion and the 1,1-(1,3-Butadienyl) Dianion

“…Arylsulfonyl bromides add to olefins photolytically to give vicinal arylsulfonyl(bromo)alkanes. 7h-j In a present method irradiation of benzenesulfonyl bromide in 14 in THF with an ordinary 500 W light bulb yields 15b (eq 5, 48%) . Similarly, p -toluenesulfonyl bromide and 14 in benzene give 24 (62%).…”

“…Halo(silyl)sulfonylbutanes such as 15a and 15b are presently prepared from 14 by addition of arylsulfonyl chlorides as catalyzed by cupric chloride (eq 5) 7a-g and by photolytic addition of arylsulfonyl bromides (eq 5) 7h…”

Photoreaction of Nitroso Compounds in Solution. Part XXXI. Mechanisms of Intramolecular Acid Catalyzed Cleavage Reactions and a Hydride Initiated Rearrangement of C-Nitroso Alkanes

“…and n.m.r. spectra of semipure fractions obtained from chromatography allowed us to identify the following compounds, 1,3-bisdimethoxymethylcyclopentane(5), 1 -formyl-3-dimethoxyrnethylcyclopentane(6) and its oxime (7), I ,3-bisformylcyclopentane (8) and its monooxime (9). These compounds2 were identified by the typical spectral data of the functional groups.…”

“…23. 2-exo-3-exo(cis-exo) and 2-exo-3-endo (trans) orientations (1)(2)(3)(4). Inspection of the literature shows that the distribution of this stereochemistry varies widely, ranging from a100X trans product on the addition ofp-tosyl chloride (7) to a 100% cis-exo product in the addition of ethyl u-bromoacetate (8). It is noteworthy that the additions of nitrosyl halides (9) and formate (10) to norbornene give the cis adducts in good yields and have been suggested to follow a four-centered addition mechanism.…”