Abstract Catalytic asymmetric total syntheses of naturally occurring C‐3a prenylated hexahydropyrrolo‐[2,3‐ b ]indoline alkaloids, such as (−)‐debromoflustramines B ( 1b ) and E 1a ), well (−)‐pseudophrynaminol 2a (−)‐pseudophrynamines 270 2c 272A 2b have been achieved via a thiourea catalyzed aldol reaction N ‐boc protected 2‐oxindole 13 with paraformaldehyde C1 unit (upto 90% ee). In this approach, (−)‐debromoflustramine was utilized an advanced intermediate for efficient pseudophrynamine...

A dynamic silver(I)-loaded [2]rotaxane shuttle (k298 = 135 kHz) was converted allosterically into a conformationally restricted due to the creation of bulky imine in center axle component. Only able catalyze 6-endo-cyclization reaction, whereas static one catalytically quiet. The mechanism catalyst deactivation elucidated.

The first asymmetric total synthesis of naturally occurring atropodiastereomers Amaryllidaceae alkaloids, such as narcipavlines A (1a) and B (1b) narcikachnines (2a) (2b), sharing a cis -dihydrobenzofuran structure is reported.

In State-I, a mixture comprising DABCO-bridged tris(zinc-porphyrin) double decker and free biped (=slider), catalysis was OFF. Acid addition (TFA or Di-Stefano fuel acid) to State-I liberated DABCO-H+ while generating highly dynamic slider-on-deck device (State-II). The released acted as base organocatalyst for Knoevenagel reaction (catalysis ON). system reversed OFF) by reducing the acidity in (by adding DBU via fuel-derived base).

Boolean operations with multiple catalysts as output are yet unknown using molecular logic. The issue is solved a two-component ensemble, composed of receptor and rotaxane, which acts three-input AND gate dual catalytic output. Actuation the ensemble by stoichiometric addition metal ions (Ag+ Cd2+) 2,2,2-trifluoroacetic acid generated in (1,1,1) truth table state catalyst duo that synergistically enabled three-step reaction, furnishing dihydroisoquinoline logic operation.

When the basic ligand 3 was added to heteroleptic three-component slider-on-deck [Ag3(1)(2)]3+ (sliding frequency k298 = 57 kHz), it operated as a moderate brake pad (k298 45 kHz). Due motion in resulting four-component [Ag3(1)(2)(3)]3+, both and silver(I) were continuously exposed became catalytically active concurrent tandem Michael addition/hydroalkoxylation.

Triphenyl phosphane (TPP) and an epoxide as a fuel system transiently transformed non-catalytic six-component turnstile into four-component catalytic rotor releasing N -methyl pyrrolidine copper( i ) complex.

The heteroleptic multi-component double slider-on-deck system DS3 exhibits tight coupling of motional speed two distinct nano-circular sliders (k298 =77 and 41 kHz) despite a 2.2 nm separation. In comparison, the single in DS1 DS2 move at vastly different =1.1 vs. 350 kHz). Synchronization motions remains even when one slows movement faster slider using small molecular brake pads. contrast to individual systems, is powerful catalyst for two-step reaction by motion both drive catalytic processes.

We demonstrate self-healing of the shuttling dynamics a molecular machine operating by negative feedback. When zinc(II) was added to copper(I)-loaded [2]rotaxane shuttle [Cu(R)]+, copper(I) replaced, thereby generating static zinc(II)-loaded [Zn(R)]2+. Loss accompanied fluorescence enhancement at λ = 364 nm. Notably, released ions catalyzed formation bis-triazole ligand, which selectively captured zinc(II). As result, restored in rotaxane, and dynamic motion [Cu(R)]+ regained. The healing...

Upon addition/removal of silver( i ) ions and due to efficient inter-component communication, a supramolecular multicomponent network acts as an OFF/ON proton relay with luminescence display enabling switchable catalysis.

Abstract A three‐component molecular ensemble consisting of the constitutionally dynamic cage 1 , rotaxane 2 and luminophore 3 acts as a signal transducer which assimilates three input signals, i. e., Zn 2+ H + Cu to perform individual logic operations (e. g. 3‐input NOR gate with catalytic output, AND optical output) operates an unconventional demultiplexer.

Herein, we demonstrate the selective dissipative and orthogonal actuation of two distinct molecular devices controlled by alternate fuel use. When multicomponent ensemble [2]rotaxane 1 turnstile [Cu(2)(3)]+ was charged with AgBF4 as chemical (Fuel 1) together NEt3/PhCH2Br (cofuels), transiently formed [Ag(1)]+ showed a stochastic shuttling silver macrocycle between degenerate triazole stations on thread (k298 = 1.2 × 105 s–1), whereas unperturbed. Instead, treatment mixture PPh3 an...

Abstract Stepwise dissipative control of two distinct motions, i.e., shuttling and sliding, is demonstrated in a single multicomponent device. When [2]rotaxane 1 , which acts as biped, deck 2 were treated with AgBF 4 /PhCH Br+NEt 3 chemical fuel, the transient catenate [Ag( )] + ⋅ [Ag ( 3+ was instantly generated showing multimodal motion autonomous return to . In process, cleanly transformed into follow‐up device ) exhibiting only sliding motion. Two interference‐free cycles proved...

Abstract Stepwise dissipative control of two distinct motions, i.e., shuttling and sliding, is demonstrated in a single multicomponent device. When [2]rotaxane 1 , which acts as biped, deck 2 were treated with AgBF 4 /PhCH Br+NEt 3 chemical fuel, the transient catenate [Ag( )] + ⋅ [Ag ( 3+ was instantly generated showing multimodal motion autonomous return to . In process, cleanly transformed into follow‐up device ) exhibiting only sliding motion. Two interference‐free cycles proved...

Abstract An efficient asymmetric approach to the ergot alkaloids has been achieved via a highly regioselective Heck cyclization. Asymmetric induction of key intermediate was catalytic enantioselective α-aminoxylation catalyzed by d-proline (98% ee). Utilizing aforementioned strategy, formal total synthesis (+)-lysergine and (+)-isolysergine achieved. Importantly, an unnatural analogues (–)-lysergine (–)-isolysergine also using l-proline.

We envisioned a novel asymmetric strategy to access unsymmetrically substituted dimeric 2-oxindoles [(

Abstract The heteroleptic multi‐component double slider‐on‐deck system DS3 exhibits tight coupling of motional speed two distinct nano‐circular sliders ( k 298 =77 and 41 kHz) despite a 2.2 nm separation. In comparison, the single in DS1 DS2 move at vastly different =1.1 vs. 350 kHz). Synchronization motions remains even when one slows movement faster slider using small molecular brake pads. contrast to individual systems, is powerful catalyst for two‐step reaction by motion both drive...