An Expeditious Preparation of 15‐Membered Nitrogen‐Containing Olefinic and Benzo Macrocycles

Abstract

(E,E)‐1,6,11‐Tris(arenesulfonyl)‐3,4‐benzo‐1,6,11‐triazacyclopentadeca‐8,13‐dienes (2) and 1,6,11‐tris(arenesulfonyl)‐3,4; 8,9;13,14‐tribenzo‐1,6,11‐triazacyclopentadecanes (3) were prepared from arenesulfonamides, trans‐1,4‐dibromobutene, and 1,2‐bis(bromomethyl)benzene. They form unstable complexes with silver tetrafluoroborate. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

15-Membered triolefinic macrocycles, their coordination chemistry with transition metals, and the catalytic properties of their palladium metal complexes. A review.

“…We have increased the family of our 15-membered macrocycles modifying the olefin precursors with the aim of studying the complexating ability of the new members of the family. Thus, we have prepared (E,E,Z)-1,6,11-tris[(2,4,6-triisopropylphenyl)sulfonyl]-1,6,11-triazacyclopentadeca-3,8,13-triene, 36, (Scheme 10), 20 (E,E)-1,6,11-tris(arenesulfonyl)-3,4-benzo-1,6,11-triazacyclopentadeca-8,13-dienes, 37 (Scheme 11), 21 and 1,6,11-tris(arenesulfonyl)-3,4;8,9;13,14-tribenzo-1,6,11-triazacyclopentadecanes, 38 (Scheme 12). 21 Macrocycle 36 featuring one cis double bond was synthesized through pathway "b" as indicated in Scheme 10.…”

“…Thus, we have prepared (E,E,Z)-1,6,11-tris[(2,4,6-triisopropylphenyl)sulfonyl]-1,6,11-triazacyclopentadeca-3,8,13-triene, 36, (Scheme 10), 20 (E,E)-1,6,11-tris(arenesulfonyl)-3,4-benzo-1,6,11-triazacyclopentadeca-8,13-dienes, 37 (Scheme 11), 21 and 1,6,11-tris(arenesulfonyl)-3,4;8,9;13,14-tribenzo-1,6,11-triazacyclopentadecanes, 38 (Scheme 12). 21 Macrocycle 36 featuring one cis double bond was synthesized through pathway "b" as indicated in Scheme 10. 20 It forms palladium(0), platinum(0), and silver(I) complexes 41, the same as its all-trans counterpart 1aaa.…”

“…Pathway "c" was followed for the synthesis of macrocycles 37 and 38. 21 In these cases trans-1,4-dibromo-2-butene was substituted by 1,2-bis(bromomethyl)benzene in the required steps (Schemes 11 and 12). This type of synthesis is versatile, and it permits once more one to combine different aryl groups at different synthetic steps.…”

Organometallic chemistry of 15-membered tri-olefinic macrocycles: catalysis by palladium(0) complexes in carbon–carbon bond-forming reactions

“…Thus, we have prepared (E,E,Z)-1,6,11-tris[(2,4,6-triisopropylphenyl) sulfonyl]-1,6,11-triazacyclopentadeca-3,8,13-triene (36) (Scheme 10) [20], (E,E)-1,6,11-tris(arenesulfonyl)-3,4-benzo-1,6,11-triazacyclopentadeca-8,13-dienes (37) (Scheme 11), [21] and 1,6,11-tris(arenesulfonyl)-3,4;8,9;13,14-tribenzo-1,6,11-triazacyclopentadecanes (38) (Scheme 11) [21].…”

“…Pathway ''c'' was followed for the synthesis of macrocycles 37 and 38 [21]. Now, 1,2-bis(bromomethyl)benzene was used in the required steps (Scheme 11).…”