Stereoselective Synthesis of 1,4,5-Tri-<i>cis</i>-guaiane Sesquiterpene: First Total Synthesis of (−)-Dendroside C Aglycon

The first total synthesis of (−)-dendroside C aglycon, consisting of a 1,4,5-tri-<i>cis</i>-guaiane skeleton, from a versatile hydroazulene intermediate has been accomplished. The key features of the syntheses include the stereoselective preparation of the unusual <i>cis</i>-hydroazulene core via a sequence of a unique Dieckmann condensation of the bicyclic lactone system, which was concisely prepared by the tandem conjugate addition and intramolecular allylic alkylation of a butenolide precursor, and construction of the characteristic tricyclic skeleton by a carbene-mediated cyclopropanation

Relationship of NLR and SUVmax with overall survival.

<p>(a) Overall survival according to NLR in all patients (N = 396): NLR <2.5: reference; NLR 2.5–4.4: HR 1.659, P<0.001; NLR ≥4.5: HR 2.926 (<i>P</i><0.001). (b) Overall survival according to the risk scores of whole patients (N = 396): Group A (score 0), group B (score 1), group C (score 2), group D (score 3). Total risk score of patients were calculated by addition of each score of NLR (score 0, NLR <2.5; score 1, 2.5≤ NLR <4.5; score 2, NLR ≥4.5) and ΔNLR (score 0: ΔNLR <0; score 1: ΔNLR ≥0). (c) Overall survival according to NLR in PET cohort (N = 118): NLR <2.5: reference; NLR 2.5–4.4: HR 2.113, P = 0.002; NLR ≥4.5: HR 3.500, P<0.001. (d) Overall survival according to SUVmax in PET cohort (N = 118): SUVmax <4.5: reference; SUVmax ≥4.5: HR 1.845, P = 0.004. (e) Overall survival according to risk scores with NLR and SUVmax in PET cohort (N = 118): Group A (score 0), group B (score 1), group C (score 2), group D (score 3). Total risk score of patients were calculated by addition of each score of NLR (score 0, NLR <2.5; score 1, 2.5≤ NLR <4.5; score 2, NLR ≥4.5) and SUVmax (score 0: SUVmax <4.5; score 1: SUVmax ≥4.5).</p