Hexanuclear Platinum(II) Thiolate Macrocyclic Host: Charge-Transfer-Driven Inclusion of a Ag^I Ion Guest

The inclusion of a Ag^I ion by a hexanuclear platinum­(II) thiolate macrocycle in solution was demonstrated, and the inclusion structure was determined by X-ray crystallography. Unique host–guest intermetallic interactions driven by charge transfer were elucidated by optical absorption spectroscopy and theoretical calculations

MOESM1 of 3-D dynamic rupture simulations of the 2016 Kumamoto, Japan, earthquake

Additional file 1. Text S1: Dynamic rupture propagation in cases with unfeasible parameters. Text S2: Effects of aseismic slip triggered by foreshock 1. Figure S1: Dynamic rupture propagation in the case with the free surface when is 100 MPa, is 50 MPa (case A), is 0.35 m, and is 1.2. Figure S2: Dynamic rupture propagation in the case with the free surface when is 100 MPa, is 50 MPa (case A), is 0.1 m, and is 0.8. Figure S3: Final slip distribution in cases C, D, and G. Figure S4: Observed and synthetic near-fault ground displacements at KMMH16 (KiK-net), 93048, and 93049 (deployed by the local government of Kumamoto prefecture) stations. Figure S5: Assumed slip distribution of the aseismic slip, ΔCFS due to the aseismic slip, and ΔCFS due to the combination of the aseismic slip and the foreshocks. Figure S6: Dynamic rupture propagation in case A2 with the free surface. The stress changes due to the aseismic slip and the foreshocks were taken into account in this simulation

Regioselective Diversification of a Cardiac Glycoside, Lanatoside C, by Organocatalysis

Acylation of lanatoside C in the presence of organocatalyst <b>5</b> gave the C(4′′′′)-<i>O</i>-acylate in up to 90% regioselectivity (catalyst-controlled regioselectivity). Various functionalized acyl groups can be introduced at the C(4′′′′)-OH by a mixed anhydride method in the presence of <b>5</b> or the related organocatalyst. On the other hand, DMAP-catalyzed acylation of lanatoside C gave the C(3′′′′)-<i>O</i>-acylate in up to 97% regioselectivity (substrate-controlled regioselectivity). Thus, diverse regioselective introduction of acyl groups among eight free hydroxy groups of lanatoside C was achieved

Origin of High <i>E</i>‑Selectivity in 4‑Pyrrolidinopyridine-Catalyzed Tetrasubstituted α,α′-Alkenediol: A Computational and Experimental Study

We have developed 4-pyrrolidinopyridine catalysts for the geometry-selective (<i>E</i>-selective) acylation of tetrasubstituted α,α′-alkenediols. To elucidate the major factors of the high geometry selectivity, experimental and computational studies were carried out. The control experiments with respect to the substituent of the substrate indicated the fundamental hydrogen bonding of the acidic hydrogen of NHNs and the <i>Z</i>-OH in the substrate. Comparison between <i>C</i>₂- and <i>C</i>₁-symmetric catalysts exhibited the necessity of the <i>C</i>₂-symmetric catalyst structure. The computationally proposed transition state (TS) model well explained the experimental results. Whereas the fundamental NH/amide-CO and the two-point free-OH/acetate anion hydrogen bonds stabilize the transition state (TS), affording the <i>E</i>-product, the steric repulsion between the N-protecting group and the amide side chain destabilizes TS, affording the <i>Z</i>-product. The role of the two amide side chains of the catalyst in a <i>C</i>₂-symmetric fashion is the enhancement of the molecular recognition ability through the additional hydrogen bond in a cooperative manner

Total Synthesis of (+)-Clavilactone A and (−)-Clavilactone B by Ring-Opening/Ring-Closing Metathesis

The enantioselective total synthesis of natural enantiomers of clavilactones A and B has been achieved. A key feature of the synthesis is the use of a ring-opening/ring-closing metathesis, which allows the one-pot transformation of a strained cyclobutenecarboxylate into a γ-butenolide

Total Synthesis of (+)-Vibsanin A

The first total synthesis of (+)-vibsanin A, an 11-membered vibsane diterpenoid, was achieved, unambiguously establishing its relative and absolute stereochemistry. Highlights of the synthesis include the stereoselective formation of an all-carbon quaternary stereocenter by a zinc-mediated Barbier-type allylation in an aqueous medium, and the efficient construction of an 11-membered ring skeleton by a combination of an intramolecular Nozaki–Hiyama–Kishi (NHK) reaction and a Mitsunobu reaction

Enantioselective Total Synthesis of (−)-Misramine

The enantioselective total synthesis of an unusual pentacyclic proaporphine alkaloid, (−)-misramine, was achieved. The synthetic strategy relied on an enantioselective intramolecular Friedel–Crafts-type 1,4-addition using an asymmetric organocatalyst to construct a spiroindane skeleton containing an all-carbon quaternary stereocenter and a double reductive amination of the keto-aldehyde to form a piperidine ring toward the end of the synthesis. This work is the first example of asymmetric synthesis of a proaporphine alkaloid

The curves of the recovery coefficients.

<p>The curves of the recovery coefficients measured by the <i>Celesteion</i> (a) and <i>Aquiduo</i> (b) scanners. The solid line with black circles corresponds to the average of the count-based measurements. The dashed line with black squares corresponds to the standard 30-min acquisition measurements.</p

Mean and standard deviation (SD) of measured SUVs.

<p>Mean and standard deviation (SD) of measured SUVs.</p

The measured SUV_max and SUV_peak of a 37-mm-diameter sphere with a 2-min acquisition over time.

<p>Standardized uptake values (SUVs) obtained from constant 2-min acquisition periods using the <i>Celesteion</i> scanner are shown over time to compare the resulting SUVs. The scatter plot depicts SUV_max (solid, black circle) and SUV_peak (empty/open circle) values. The solid and dotted trend lines correspond to SUV_max and SUV_peak, respectively.</p