Facile Synthesis of New Polyazamacrocycles by the Pd-Catalyzed Amination of 3,3'-Dibromobiphenyl

Abstract

Pd-Catalyzed amination of 3,3'-dibromobiphenyl using various

Pd-catalyzed amination of dibromobiphenyls in the synthesis of macrocycles comprising two biphenyl and two polyamine moieties

“…In all cases the formation of the macrocycles 12 containing one set of biphenyl and polyamine units was observed, and with longer trioxadiamine 2c and tetraamine 2d their yields were about 40% which is equal to the yields of these compounds when the reactions were run with equimolar amounts of starting compounds. 31 Higher mass cyclooligomers were also formed in the case of dioxadiamine 2b and trioxadiamine 2c.…”

“…The reaction of equimolar amounts of 1,3-diaminopropane 2a with 3,3'-dibromobiphenyl 9 described by us previously afforded 24% yield of the cyclic dimer 11a. 31 Thus it is clear that the approach via in situ obtained N,N'-bis(3-bromobiphenyl)diamine is not suitable for this compound.…”

“…30, and spectral data for compounds 11a-d, 12b-d and 13c (n=2) are given in ref. 31. Standard method for the synthesis of N,N'-bis(bromobiphenyl)polyamines 3a-d and 10b-d. A two-neck flask equipped with a magnetic stirrer, flushed with dry argon was charged with 4,4'-dibromobiphenyl 1 or 3,3'-dibromobiphenyl 9 (2.2 mmol, 686 mg), Pd(dba) 2 (0.04 mmol, 23 mg), BINAP (0.045 mmol, 28 mg), absolute dioxane (10 ml), the mixture was stirred for 2 min, then appropriate polyamine 2a-d (1 mmol) was added, followed by tBuONa (3 mmol, 290 mg).…”

Contribution of I. P. Beletskaya in the Twentieth Year Successful Russian-French Cooperation in Catalytic Syntheses

“…Above mentioned macrocycles based on 2,7-disubstituted naphthalene and 3,3'-disubstituted biphenyl moieties were modified with two bromobenzyl fragments followed by macrocyclization with various polyamines and oxadiamines to provide corresponding cryptands in yields up to 30-35 %. [35,36] Much more versatile cryptands were synthesized on the basis of trans-N,N'-di(bromobenzyl) substituted cyclen and cyclam. At first the scope and limitations of this approach were determined to demonstrate the possibility of the synthesis of the cryptands in yields up to 45 %, the formation of interesting by-products, cylindrically shaped macrotricycles, was noted in many cases.…”

“…Similar protocols were applied to the synthesis of biphenyl-containing macrocycles which were synthesized in yields up to 44 %. [15][16][17] It should be noted that in every case the dependence of the reaction outcome on the structure of polyamines was investigated.…”