Asymmetric total syntheses of ansamacrolactams (+)-Q-1047H-A-A and (+)-Q-1047H-R-A.
The total syntheses of ansamacrolactams (+)-Q-1047H-A-A (16) and (+)-Q-1047H-R-A (17) have been achieved for the first time in 17 steps, leading to the reassignment of the relative stereochemistries and absolute configurations of their natural counterparts. The key steps in the synthetic work included an asymmetric chelation-controlled vinylogous Mukaiyama aldol reaction for the stereoselective synthesis of the syn-aldol adduct 7b and an intramolecular SmI(2)-mediated Reformatsky reaction for the formation of the macrocyclic lactam 14.
Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, and Peking-Tsinghua Center for Life Sciences, Peking University, Beijing 100871, China.
Shouliang
S
Yang
Yumeng
Y
Xi
Rong
R
Zhu
Lin
L
Wang
Jiahua
J
Chen
Zhen
Z
Yang
D006094:Gram-Positive Bacteria / Q000737:chemistry; D007769:Lactams / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D013237:Stereoisomerism
D007769:Lactams; C581592:Q-1047H-A-A; C581593:Q-1047H-R-A