TY - JOUR
T1 - Total synthesis and configurational assignment of chondramide A
AU - Schmauder, Anke
AU - Sibley, L. David
AU - Maier, Martin E.
PY - 2010/4/12
Y1 - 2010/4/12
N2 - The first total synthesis of the cyclodepsipeptide chondramide A (2b) is described. This depsipeptide is composed of four subunits, namely Lalanine, N-Me-D-tryptophan, 3-amino-2-methoxy-propionic acid (β-tyrosine derivative), and a 7-hydroxy-alkenoic acid. While the configuration of the stereogenic centers in the 7-hydroxy-alkenoic acid were known, the configuration of the tyrosine derivative required clarification and turned out to be (2S,3R) or (2L,3L), respectively. The synthesis of the 3-amino-2-methoxy-3-arylpropanoic ester 20 b relied on an asymmetric dihydroxylation yielding diol ent-15a followed by a regioselective Mitsunobu substitution leading to 3-azido-2-hydroxypropanoate 18 b. We could also show that the ester bond in the seco compound 26b can be fashioned by a Mitsunobu esterification by using hydroxy ester (7S)-7 and the tripeptide acid 25 b. This synthesis should allow for the preparation of various analogues.
AB - The first total synthesis of the cyclodepsipeptide chondramide A (2b) is described. This depsipeptide is composed of four subunits, namely Lalanine, N-Me-D-tryptophan, 3-amino-2-methoxy-propionic acid (β-tyrosine derivative), and a 7-hydroxy-alkenoic acid. While the configuration of the stereogenic centers in the 7-hydroxy-alkenoic acid were known, the configuration of the tyrosine derivative required clarification and turned out to be (2S,3R) or (2L,3L), respectively. The synthesis of the 3-amino-2-methoxy-3-arylpropanoic ester 20 b relied on an asymmetric dihydroxylation yielding diol ent-15a followed by a regioselective Mitsunobu substitution leading to 3-azido-2-hydroxypropanoate 18 b. We could also show that the ester bond in the seco compound 26b can be fashioned by a Mitsunobu esterification by using hydroxy ester (7S)-7 and the tripeptide acid 25 b. This synthesis should allow for the preparation of various analogues.
KW - Amino acids
KW - Asymmetric synthesis
KW - Cyclodepsipeptides
KW - Natural products
KW - Peptides
UR - http://www.scopus.com/inward/record.url?scp=77950850810&partnerID=8YFLogxK
U2 - 10.1002/chem.200903500
DO - 10.1002/chem.200903500
M3 - Article
C2 - 20222097
AN - SCOPUS:77950850810
SN - 0947-6539
VL - 16
SP - 4328
EP - 4336
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 14
ER -