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The Soai reaction has profoundly impacted chemists' perspective of autocatalysis, chiral symmetry breaking, absolute asymmetric synthesis and its role in the origin of biological homochirality. Here we describe the unprecedented observation of asymmetry-amplifying autocatalysis in the alkylation of 5-(trimethylsilylethynyl)pyridine-3-carbaldehyde using diisopropylzinc. Kinetic studies with a surrogate substrate and spectroscopic analysis of a series of zinc alkoxides that incorporate specific structural mutations reveal a 'pyridine-assisted cube escape'. The new tetrameric cluster functions as a catalyst that activates the substrate through a two-point binding mode and poises a coordinated diisopropylzinc moiety for alkyl group transfer. Transition-state models leading to both the homochiral and heterochiral products were validated by density functional theory calculations. Moreover, experimental and computational analysis of the heterochiral complex provides a definitive explanation for the nonlinear behaviour of this system. Our deconstruction of the Soai system reveals the structural logic for autocatalyst evolution, function and substrate compatibility-a central mechanistic aspect of this iconic transformation.
This article was published in the following journal.
Name: Nature chemistry
DNAzymes have been recognized as promising transducing agents for visualizing endogenous biomarkers, while their inefficient intracellular delivery (including blunt responsibility) and limited amplifi...
Due to their inconspicuous behaviour and colouration, it has been assumed that titi monkeys' main anti-predator behaviour is passive crypsis and hiding. So far, active predator mobbing has been docume...
Previous work has shown that dampening appraisals (e.g., thinking "this is too good to last") reduce happiness and enhance sadness when adults recall positive events. In contrast, amplifying appraisal...
The critical region in the phase diagram of condensed matter systems such as fluids or fluid mixtures is characterized by the anomalous behaviour of specific thermodynamic properties. Here, we discuss...
A marked asymmetry was previously reported in the sacral alae and S1-L5 facets orientation of the Neandertal individual Regourdou 1. Here, we provide a detailed description and quantification of the m...
The major problem in stroke survivors that is being addressed in this research project is walking asymmetry, i.e., difference between the legs during walking (e.g. steps on the more affect...
Humans generally develop a preferred upper and lower extremity. Due to repetitive uneven loading, this gradually results in structural (e.g. increased bone and muscle mass) and functional ...
This prospective, randomized, controlled trial is proposed to investigate the effect of OMT on sacral base asymmetry as assessed by ultrasound.
This study will investigate the relationship between sedentary behaviour and subjective well-being among a sample of university students. Eligible participants will fill out an online surv...
In hemiplegia quantitatively measurement of the asymmetry in the use of upper limbs could overcome the limitation of many outcome measures in which scores are dependent on the experience a...
Congenital or acquired asymmetry of the face.
The excision of in-frame internal protein sequences (INTEINS) of a precursor protein, coupled with ligation of the flanking sequences (EXTEINS). Protein splicing is an autocatalytic reaction and results in the production of two proteins from a single primary translation product: the intein and the mature protein.
Methods for using more than one primer set in a polymerase chain reaction to amplify more than one segment of the target DNA sequence in a single reaction.
Methods used for detecting the amplified DNA products from the polymerase chain reaction as they accumulate instead of at the end of the reaction.
Wearable sound-amplifying devices that are intended to compensate for impaired hearing. These generic devices include air-conduction hearing aids and bone-conduction hearing aids. (UMDNS, 1999)
Biological therapy involves the use of living organisms, substances derived from living organisms, or laboratory-produced versions of such substances to treat disease. Some biological therapies for cancer use vaccines or bacteria to stimulate the body&rs...