An Approach to the Regioselective Diamination of Conjugated Di‐ and Trienes

Abstract

It's do or diaminate: The selective diamination of 1,3-butadienes in the presence of hypervalent iodine reagents has been developed. This oxidation process proceeds with complete selectivity in favor of diamination. Depending on the substrate, it proceeds either with 1,2- or 1,4-regioselectivity (see scheme).

Dioxoiodane Compounds as Versatile Sources for Iodine(I) Chemistry

“…Furtherr eactivity was explored for additional substrates such as the 1,3-butadiene 11 a (Scheme 8). As expected from ar elated diamination with hypervalent iodine reagents, [23] the reactionw ith 3e led to the formation of as ingler egioisomeric product 12 a,w hich is the thermodynamically preferred product due to maintenance of the styrene conjugation.2 -Aminostyrene also constitutes an interesting substrate. While its Cbzprotectedd erivative 4t behaves as the styrene derivatives from Scheme 5a nd thus undergoes clean iodooxygenation to 6r,t he corresponding tosylamide 4s promotes an aminooxygenationt ot he 3-oxygenated indoline 12 b.I nterestingly, this product proofed to be stable against indole formation [24] through elimination.…”

Organoselenium‐Catalyzed Regioselective C−H Pyridination of 1,3‐Dienes and Alkenes

“…[17] It is noteworthy that ahalogen substituent tolerated the reaction conditions (2h,6 0%). [17] It is noteworthy that ahalogen substituent tolerated the reaction conditions (2h,6 0%).…”

The Divergent Synthesis of Nitrogen Heterocycles by Rhodium(II)‐Catalyzed Cycloadditions of 1‐Sulfonyl 1,2,3‐Triazoles with 1,3‐Dienes

“…As a result, we report herein the first rhodium(II)-catalyzed aza-[4+3] cycloadditions of 1-sulfonyl 1,2,3-triazoles with 1,3-dienes, a reaction enabling the efficient synthesis of highly functionalized 2,5dihydroazepines from readily available precursors (Figure 1 c). Notably, in some cases the reaction pathway could [*] Dr. H. Shang, [+] Y. Wang, [+] [14] We initiated our study by treatment of the readily accessible triazole 1 a [15] and (E)-1-phenyl-1,3-butadiene (2 a) [16] with 1 mol % [Rh 2 (oct) 4 ] in 1,2-DCE at 120 8C for 12 hours. Fortunately, two major products formed, and one of them, isolated in 37 % yield, was unambiguously confirmed as the aza-[4+3] cycloadduct 3 a by X-ray crystallography (Scheme 1).…”