Selective protection of mixed primary–secondary amines. Simple preparation of N¹,N⁸-bis(t-butoxycarbonyl)spermidine

Selective protection of polyamines: synthesis of model compounds and spermidine derivatives

“…The crystallized specimen was identical with the product prepared according to procedure (A). N',N4,N8-Z,-Spermidine (7).-This compound was prepared from spermidine on a 10 mmol scale essentially as described for (2a). The yield of chromatographed material, obtained as a pale yellow oil, pure by t. N ' ,N8-Boc, -N ' ,N4,N8 -Z,-spermidine (8).-The t -bu t oxycarbonylation of compound (7) was achieved as described for (2a).…”

“…N',N4,N8-Z,-Spermidine (7).-This compound was prepared from spermidine on a 10 mmol scale essentially as described for (2a). The yield of chromatographed material, obtained as a pale yellow oil, pure by t. N ' ,N8-Boc, -N ' ,N4,N8 -Z,-spermidine (8).-The t -bu t oxycarbonylation of compound (7) was achieved as described for (2a). The crude product was chromatographed on silica (CH,Cl,-Et,O, 20: 1) to give Boc,-Z,-spermidine (8) as a pale yellow oil (7.6 g, 92%); pure by t.…”

Di-t-butyl Dicarbonate

“…t-Butoxycarbonylation of a N,N -bis(benzyloxycarbonyl)diamine followed by hydrogenolysis of the Cbz groups furnishes the tbutoxycarbonylated derivative of the primary amino function (eq 24). 84 Analogous strategies have been used for the selective indirect acylation of polyamines such as spermidine. 85 The t-butoxycarbonylation of the sodium salt of thiourea does not require DMAP catalysis.…”

Novel Gabriel reagents

“…N-Alkylated benzyl íerí-butyl imidodicarbonates are known to cleave selectively by catalytic hydrogenolysis just like ordinary compounds containing simultaneously benzyl and íerí-butyl carbamate groups. 35 ieri-Butyl ondary amines by two-step alkylations. As earlier mentioned, one Boc group can also be selectively removed from compounds derived from 2, and therefore the imidodicarbonate 2 is equally useful.…”