Total Synthesis of Glycocinnasperimicin D

Abstract

A three‐fragment coupling strategy afforded the antibiotic glycocinnasperimicin D (1). The convergent total synthesis features a Heck reaction to form the cinnamoyl glycoside, the [3,3] sigmatropic rearrangement of an allyl cyanate for the stereoselective synthesis of the allyl amine, and the coupling of a glycosyl isocyanate with an amino sugar for the construction of the urea glycoside linkage.

Cutting-Edge and Time-Honored Strategies for Stereoselective Construction of C–N Bonds in Total Synthesis

“…Dehydration under Appel’s conditions (CBr 4 , PPh 3 , Et 3 N, CH 2 Cl 2 , −10 °C) afforded the allylic cyanate, which underwent an instantaneous rearrangement and a subsequent trapping with trichloroethanol to produce carbamate 176 - 5 in 75% overall yield over four steps. The Ichikawa group also used a similar approach to introduce the C–N bond at an early stage in the synthesis of glycocinnasperimicin D. , …”

Transition metals in organic synthesis: Highlights for the year 2005

“…The intermolecular Heck reaction was used in organic synthesis of, for example, glycocinnasperimicin D [426], cribrostatin IV [427], novel pyrimidine nucleosides [428], ␣ v ␤ 3 antagonist [215], KDR kinase inhibitors [376], selaginoidine [429], pancracine [430], pyrrolidino pseudoisocytidine [431], (+)-and (−)-deplanchein [230], rhizoxin D [432], 2-acetonylinosine [433] and 10-deoxyartemisinins [434]. A combination of an intermolecular and intramolecular Heck reaction of iodoarylalkenes was used to prepare macrocycles [435].…”

[3,3]-Sigmatropic rearrangements: recent applications in the total synthesis of natural products

“…In a recent total synthesis of glycocinnasperimicin D, 32 an unusual hetero-Cope rearrangement has been used to install an amino-group of one of the carbohydrate building blocks. As illustrated in Scheme 25, cyanate 209 obtained by dehydration of carbamate 208 underwent an efficient low-temperature sigmatropic transposition to isocyanate 210 , which was trapped with trichloroethyl alcohol to give protected allylic amine 211 in an 82% overall yield.…”