Mini-ISES identifies promising carbafructopyranose-based salens for asymmetric catalysis: Tuning ligand shape via the anomeric effect.

Abstract:

:This study introduces new methods of screening for and tuning chiral space and in so doing identifies a promising set of chiral ligands for asymmetric synthesis. The carbafructopyranosyl-1,2-diamine(s) and salens constructed therefrom are particularly compelling. It is shown that by removing the native anomeric effect in this ligand family, one can tune chiral ligand shape and improve chiral bias. This concept is demonstrated by a combination of (i) x-ray crystallographic structure determination, (ii) assessment of catalytic performance, and (iii) consideration of the anomeric effect and its underlying dipolar basis. The title ligands were identified by a new mini version of the in situ enzymatic screening (ISES) procedure through which catalyst-ligand combinations are screened in parallel, and information on relative rate and enantioselectivity is obtained in real time, without the need to quench reactions or draw aliquots. Mini-ISES brings the technique into the nanomole regime (200 to 350 nmol catalyst/20 μml organic volume) commensurate with emerging trends in reaction development/process chemistry. The best-performing β-d-carbafructopyranosyl-1,2-diamine-derived salen ligand discovered here outperforms the best known organometallic and enzymatic catalysts for the hydrolytic kinetic resolution of 3-phenylpropylene oxide, one of several substrates examined for which the ligand is "matched." This ligand scaffold defines a new swath of chiral space, and anomeric effect tunability defines a new concept in shaping that chiral space. Both this ligand set and the anomeric shape-tuning concept are expected to find broad application, given the value of chiral 1,2-diamines and salens constructed from these in asymmetric catalysis.

journal_name

Sci Adv

journal_title

Science advances

authors

Karukurichi KR,Fei X,Swyka RA,Broussy S,Shen W,Dey S,Roy SK,Berkowitz DB

doi

10.1126/sciadv.1500066

subject

Has Abstract

pub_date

2015-07-01 00:00:00

issue

6

issn

2375-2548

journal_volume

1

pub_type

杂志文章
  • An alternate conformation of HCV E2 neutralizing face as an additional vaccine target.

    abstract::To achieve global elimination of hepatitis C virus (HCV), an effective cross-genotype vaccine is needed. The HCV envelope glycoprotein E2 is the main target for neutralizing antibodies (nAbs), which aid in HCV clearance and protection. E2 is structurally flexible and functions in engaging host receptors. Many nAbs bin...

    journal_title:Science advances

    pub_type: 杂志文章

    doi:10.1126/sciadv.abb5642

    authors: Tzarum N,Giang E,Kadam RU,Chen F,Nagy K,Augestad EH,Velázquez-Moctezuma R,Keck ZY,Hua Y,Stanfield RL,Dreux M,Prentoe J,Foung SKH,Bukh J,Wilson IA,Law M

    更新日期:2020-07-24 00:00:00

  • Strong coupling superconductivity in a quasiperiodic host-guest structure.

    abstract::We examine the low-temperature states supported by the quasiperiodic host-guest structure of elemental bismuth at high pressure, Bi-III. Our electronic transport and magnetization experiments establish Bi-III as a rare example of type II superconductivity in an element, with a record upper critical field of ~ 2.5 T, u...

    journal_title:Science advances

    pub_type: 杂志文章

    doi:10.1126/sciadv.aao4793

    authors: Brown P,Semeniuk K,Wang D,Monserrat B,Pickard CJ,Grosche FM

    更新日期:2018-04-13 00:00:00

  • Direct 4D printing via active composite materials.

    abstract::We describe an approach to print composite polymers in high-resolution three-dimensional (3D) architectures that can be rapidly transformed to a new permanent configuration directly by heating. The permanent shape of a component results from the programmed time evolution of the printed shape upon heating via the desig...

    journal_title:Science advances

    pub_type: 杂志文章

    doi:10.1126/sciadv.1602890

    authors: Ding Z,Yuan C,Peng X,Wang T,Qi HJ,Dunn ML

    更新日期:2017-04-12 00:00:00

  • Chemical trigger toward phase separation in the aqueous Al(III) system revealed.

    abstract::Although Al(III) hydrolysis, condensation, and nucleation play pivotal roles in the synthesis of Al-based compounds and determine their chemical behavior, we still lack experimental evidence regarding the chemistry of nucleation from solution. Here, by combining advanced titration assays, high-resolution transmission ...

    journal_title:Science advances

    pub_type: 杂志文章

    doi:10.1126/sciadv.aba6878

    authors: Lukić MJ,Wiedenbeck E,Reiner H,Gebauer D

    更新日期:2020-06-03 00:00:00

  • Saigas on the brink: Multidisciplinary analysis of the factors influencing mass mortality events.

    abstract::In 2015, more than 200,000 saiga antelopes died in 3 weeks in central Kazakhstan. The proximate cause of death is confirmed as hemorrhagic septicemia caused by the bacterium Pasteurella multocida type B, based on multiple strands of evidence. Statistical modeling suggests that there was unusually high relative humidit...

    journal_title:Science advances

    pub_type: 杂志文章

    doi:10.1126/sciadv.aao2314

    authors: Kock RA,Orynbayev M,Robinson S,Zuther S,Singh NJ,Beauvais W,Morgan ER,Kerimbayev A,Khomenko S,Martineau HM,Rystaeva R,Omarova Z,Wolfs S,Hawotte F,Radoux J,Milner-Gulland EJ

    更新日期:2018-01-17 00:00:00

  • Refined symmetry indicators for topological superconductors in all space groups.

    abstract::Topological superconductors are exotic phases of matter featuring robust surface states that could be leveraged for topological quantum computation. A useful guiding principle for the search of topological superconductors is to relate the topological invariants with the behavior of the pairing order parameter on the n...

    journal_title:Science advances

    pub_type: 杂志文章

    doi:10.1126/sciadv.aaz8367

    authors: Ono S,Po HC,Watanabe H

    更新日期:2020-05-01 00:00:00

  • Biodiversity enhances the multitrophic control of arthropod herbivory.

    abstract::Arthropod herbivores cause substantial economic costs that drive an increasing need to develop environmentally sustainable approaches to herbivore control. Increasing plant diversity is expected to limit herbivory by altering plant-herbivore and predator-herbivore interactions, but the simultaneous influence of these ...

    journal_title:Science advances

    pub_type: 杂志文章

    doi:10.1126/sciadv.abb6603

    authors: Barnes AD,Scherber C,Brose U,Borer ET,Ebeling A,Gauzens B,Giling DP,Hines J,Isbell F,Ristok C,Tilman D,Weisser WW,Eisenhauer N

    更新日期:2020-11-06 00:00:00

  • Structure and dynamical behavior of non-normal networks.

    abstract::We analyze a collection of empirical networks in a wide spectrum of disciplines and show that strong non-normality is ubiquitous in network science. Dynamical processes evolving on non-normal networks exhibit a peculiar behavior, as initial small disturbances may undergo a transient phase and be strongly amplified in ...

    journal_title:Science advances

    pub_type: 杂志文章

    doi:10.1126/sciadv.aau9403

    authors: Asllani M,Lambiotte R,Carletti T

    更新日期:2018-12-12 00:00:00

  • Graphene catalyzes the reversible formation of a C-C bond between two molecules.

    abstract::Carbon deposits are well-known inhibitors of transition metal catalysts. In contrast to this undesirable behavior, here we show that epitaxial graphene grown on Ru(0001) promotes the reversible formation of a C-C bond between -CH2CN and 7,7,8,8-tetracyano-p-quinodimethane (TCNQ). The catalytic role of graphene is mult...

    journal_title:Science advances

    pub_type: 杂志文章

    doi:10.1126/sciadv.aau9366

    authors: Navarro JJ,Pisarra M,Nieto-Ortega B,Villalva J,Ayani CG,Díaz C,Calleja F,Miranda R,Martín F,Pérez EM,Vázquez de Parga AL

    更新日期:2018-12-14 00:00:00

  • Electrodeposited surfaces with reversibly switching interfacial properties.

    abstract::Engineered surfaces with reversibly switching interfacial properties, such as wettability and liquid repellency, are highly desirable in diverse application fields but are rare. We have developed a general concept to prepare metallic porous surfaces with exceptionally powerful wettability switch capabilities and liqui...

    journal_title:Science advances

    pub_type: 杂志文章

    doi:10.1126/sciadv.aax0380

    authors: Liu Y,Zhao L,Lin J,Yang S

    更新日期:2019-11-01 00:00:00

  • Wearable/disposable sweat-based glucose monitoring device with multistage transdermal drug delivery module.

    abstract::Electrochemical analysis of sweat using soft bioelectronics on human skin provides a new route for noninvasive glucose monitoring without painful blood collection. However, sweat-based glucose sensing still faces many challenges, such as difficulty in sweat collection, activity variation of glucose oxidase due to lact...

    journal_title:Science advances

    pub_type: 杂志文章

    doi:10.1126/sciadv.1601314

    authors: Lee H,Song C,Hong YS,Kim MS,Cho HR,Kang T,Shin K,Choi SH,Hyeon T,Kim DH

    更新日期:2017-03-08 00:00:00

  • Coming out in STEM: Factors affecting retention of sexual minority STEM students.

    abstract::Using a national longitudinal survey data set from the Higher Education Research Institute, this study tested whether students who identified as a sexual minority (for example, lesbian, gay, bisexual, or queer) were more or less likely to persist after 4 years in science, technology, engineering, and mathematics (STEM...

    journal_title:Science advances

    pub_type: 杂志文章

    doi:10.1126/sciadv.aao6373

    authors: Hughes BE

    更新日期:2018-03-14 00:00:00

  • Role of Ca2+ transients at the node of the mouse embryo in breaking of left-right symmetry.

    abstract::Immotile cilia sense extracellular signals such as fluid flow, but whether Ca2+ plays a role in flow sensing has been unclear. Here, we examined the role of ciliary Ca2+ in the flow sensing that initiates the breaking of left-right (L-R) symmetry in the mouse embryo. Intraciliary and cytoplasmic Ca2+ transients were d...

    journal_title:Science advances

    pub_type: 杂志文章

    doi:10.1126/sciadv.aba1195

    authors: Mizuno K,Shiozawa K,Katoh TA,Minegishi K,Ide T,Ikawa Y,Nishimura H,Takaoka K,Itabashi T,Iwane AH,Nakai J,Shiratori H,Hamada H

    更新日期:2020-07-22 00:00:00

  • In vivo mapping of tissue- and subcellular-specific proteomes in Caenorhabditis elegans.

    abstract::Multicellular organisms are composed of tissues that have distinct functions requiring specialized proteomes. To define the proteome of a live animal with tissue and subcellular resolution, we adapted a localized proteomics technology for use in the multicellular model organism Caenorhabditis elegans. This approach co...

    journal_title:Science advances

    pub_type: 杂志文章

    doi:10.1126/sciadv.1602426

    authors: Reinke AW,Mak R,Troemel ER,Bennett EJ

    更新日期:2017-05-10 00:00:00

  • Direct observation of Σ7 domain boundary core structure in magnetic skyrmion lattice.

    abstract::Skyrmions are topologically protected nanoscale magnetic spin entities in helical magnets. They behave like particles and tend to form hexagonal close-packed lattices, like atoms, as their stable structure. Domain boundaries in skyrmion lattices are considered to be important as they affect the dynamic properties of m...

    journal_title:Science advances

    pub_type: 杂志文章

    doi:10.1126/sciadv.1501280

    authors: Matsumoto T,So YG,Kohno Y,Sawada H,Ikuhara Y,Shibata N

    更新日期:2016-02-12 00:00:00

  • Dependence of drivers affects risks associated with compound events.

    abstract::Compound climate extremes are receiving increasing attention because of their disproportionate impacts on humans and ecosystems. However, risks assessments generally focus on univariate statistics. We analyze the co-occurrence of hot and dry summers and show that these are correlated, inducing a much higher frequency ...

    journal_title:Science advances

    pub_type: 杂志文章

    doi:10.1126/sciadv.1700263

    authors: Zscheischler J,Seneviratne SI

    更新日期:2017-06-28 00:00:00

  • Acupuncture attenuates alcohol dependence through activation of endorphinergic input to the nucleus accumbens from the arcuate nucleus.

    abstract::A withdrawal-associated impairment in β-endorphin neurotransmission in the arcuate nucleus (ARC) of the hypothalamus is associated with alcohol dependence characterized by a chronic relapsing disorder. Although acupuncture activates β-endorphin neurons in the ARC projecting to the nucleus accumbens (NAc), a role for A...

    journal_title:Science advances

    pub_type: 杂志文章

    doi:10.1126/sciadv.aax1342

    authors: Chang S,Kim DH,Jang EY,Yoon SS,Gwak YS,Yi YJ,Lee JY,Ahn SH,Kim JM,Ryu YH,Kim SN,Roh HS,Lee MY,Kim SC,Lee BH,Kim HY,Yang CH

    更新日期:2019-09-04 00:00:00

  • The limits of earthquake early warning: Timeliness of ground motion estimates.

    abstract::The basic physics of earthquakes is such that strong ground motion cannot be expected from an earthquake unless the earthquake itself is very close or has grown to be very large. We use simple seismological relationships to calculate the minimum time that must elapse before such ground motion can be expected at a dist...

    journal_title:Science advances

    pub_type: 杂志文章

    doi:10.1126/sciadv.aaq0504

    authors: Minson SE,Meier MA,Baltay AS,Hanks TC,Cochran ES

    更新日期:2018-03-21 00:00:00

  • Delivery of RIPK4 small interfering RNA for bladder cancer therapy using natural halloysite nanotubes.

    abstract::RNA interference (RNAi) technology can specifically silence the expression of a target gene and has emerged as a promising therapeutic method to treat cancer. In the present study, we showed that natural halloysite nanotube (HNT)-assisted delivery of an active small interfering RNA (siRNA) targeting receptor-interacti...

    journal_title:Science advances

    pub_type: 杂志文章

    doi:10.1126/sciadv.aaw6499

    authors: Liu J,Zhang Y,Zeng Q,Zeng H,Liu X,Wu P,Xie H,He L,Long Z,Lu X,Xiao M,Zhu Y,Bo H,Cao K

    更新日期:2019-09-25 00:00:00

  • A stability-reversibility map unifies elasticity, plasticity, yielding, and jamming in hard sphere glasses.

    abstract::Amorphous solids, such as glasses, have complex responses to deformations, with substantial consequences in material design and applications. In this respect, two intertwined aspects are important: stability and reversibility. It is crucial to understand, on the one hand, how a glass may become unstable due to increas...

    journal_title:Science advances

    pub_type: 杂志文章

    doi:10.1126/sciadv.aat6387

    authors: Jin Y,Urbani P,Zamponi F,Yoshino H

    更新日期:2018-12-07 00:00:00

  • Micronutrient-fortified rice can be a significant source of dietary bioavailable iron in schoolchildren from rural Ghana.

    abstract::Iron deficiency and anemia are prominent contributors to the preventable disease burden worldwide. A substantial proportion of people with inadequate dietary iron rely on rice as a staple food, but fortification efforts are limited by low iron bioavailability. Furthermore, using high iron fortification dosages may not...

    journal_title:Science advances

    pub_type: 杂志文章

    doi:10.1126/sciadv.aau0790

    authors: Hackl LS,Abizari AR,Speich C,Zungbey-Garti H,Cercamondi CI,Zeder C,Zimmermann MB,Moretti D

    更新日期:2019-03-27 00:00:00

  • Direct quantitative measurement of the C═O⋅⋅⋅H-C bond by atomic force microscopy.

    abstract::The hydrogen atom-the smallest and most abundant atom-is of utmost importance in physics and chemistry. Although many analysis methods have been applied to its study, direct observation of hydrogen atoms in a single molecule remains largely unexplored. We use atomic force microscopy (AFM) to resolve the outermost hydr...

    journal_title:Science advances

    pub_type: 杂志文章

    doi:10.1126/sciadv.1603258

    authors: Kawai S,Nishiuchi T,Kodama T,Spijker P,Pawlak R,Meier T,Tracey J,Kubo T,Meyer E,Foster AS

    更新日期:2017-05-12 00:00:00

  • Evolution of metabolic novelty: A trichome-expressed invertase creates specialized metabolic diversity in wild tomato.

    abstract::Plants produce a myriad of taxonomically restricted specialized metabolites. This diversity-and our ability to correlate genotype with phenotype-makes the evolution of these ecologically and medicinally important compounds interesting and experimentally tractable. Trichomes of tomato and other nightshade family plants...

    journal_title:Science advances

    pub_type: 杂志文章

    doi:10.1126/sciadv.aaw3754

    authors: Leong BJ,Lybrand DB,Lou YR,Fan P,Schilmiller AL,Last RL

    更新日期:2019-04-24 00:00:00

  • Monolithic shape-programmable dielectric liquid crystal elastomer actuators.

    abstract::Soft robotics may enable many new technologies in which humans and robots physically interact, yet the necessary high-performance soft actuators still do not exist. The optimal soft actuators need to be fast and forceful and have programmable shape changes. Furthermore, they should be energy efficient for untethered a...

    journal_title:Science advances

    pub_type: 杂志文章

    doi:10.1126/sciadv.aay0855

    authors: Davidson ZS,Shahsavan H,Aghakhani A,Guo Y,Hines L,Xia Y,Yang S,Sitti M

    更新日期:2019-11-22 00:00:00

  • Negative-pressure polymorphs made by heterostructural alloying.

    abstract::The ability of a material to adopt multiple structures, known as polymorphism, is a fascinating natural phenomenon. Various polymorphs with unusual properties are routinely synthesized by compression under positive pressure. However, changing a material's structure by applying tension under negative pressure is much m...

    journal_title:Science advances

    pub_type: 杂志文章

    doi:10.1126/sciadv.aaq1442

    authors: Siol S,Holder A,Steffes J,Schelhas LT,Stone KH,Garten L,Perkins JD,Parilla PA,Toney MF,Huey BD,Tumas W,Lany S,Zakutayev A

    更新日期:2018-04-20 00:00:00

  • High-speed imaging of ice nucleation in water proves the existence of active sites.

    abstract::Understanding how surfaces direct nucleation is a complex problem that limits our ability to predict and control crystal formation. We here address this challenge using high-speed imaging to identify and quantify the sites at which ice nucleates in water droplets on the two natural cleavage faces of macroscopic feldsp...

    journal_title:Science advances

    pub_type: 杂志文章

    doi:10.1126/sciadv.aav4316

    authors: Holden MA,Whale TF,Tarn MD,O'Sullivan D,Walshaw RD,Murray BJ,Meldrum FC,Christenson HK

    更新日期:2019-02-01 00:00:00

  • Nanoparticles that do not adhere to mucus provide uniform and long-lasting drug delivery to airways following inhalation.

    abstract::Mucoadhesive particles (MAP) have been widely explored for pulmonary drug delivery because of their perceived benefits in improving particle residence in the lungs. However, retention of particles adhesively trapped in airway mucus may be limited by physiologic mucus clearance mechanisms. In contrast, particles that a...

    journal_title:Science advances

    pub_type: 杂志文章

    doi:10.1126/sciadv.1601556

    authors: Schneider CS,Xu Q,Boylan NJ,Chisholm J,Tang BC,Schuster BS,Henning A,Ensign LM,Lee E,Adstamongkonkul P,Simons BW,Wang SS,Gong X,Yu T,Boyle MP,Suk JS,Hanes J

    更新日期:2017-04-05 00:00:00

  • Pharmacologic inhibition of JAK-STAT signaling promotes hair growth.

    abstract::Several forms of hair loss in humans are characterized by the inability of hair follicles to enter the growth phase (anagen) of the hair cycle after being arrested in the resting phase (telogen). Current pharmacologic therapies have been largely unsuccessful in targeting pathways that can be selectively modulated to i...

    journal_title:Science advances

    pub_type: 杂志文章

    doi:10.1126/sciadv.1500973

    authors: Harel S,Higgins CA,Cerise JE,Dai Z,Chen JC,Clynes R,Christiano AM

    更新日期:2015-10-23 00:00:00

  • A natural experiment reveals the impact of hydroelectric dams on the estuaries of tropical rivers.

    abstract::We tested how sediment trapping by hydroelectric dams affects tropical estuaries by comparing two dammed and two undammed rivers on Mexico's Pacific coast. We found that dams demonstrably affected the stability and productivity of the estuaries. The two rivers dammed for hydroelectricity had a rapid coastal recession ...

    journal_title:Science advances

    pub_type: 杂志文章

    doi:10.1126/sciadv.aau9875

    authors: Ezcurra E,Barrios E,Ezcurra P,Ezcurra A,Vanderplank S,Vidal O,Villanueva-Almanza L,Aburto-Oropeza O

    更新日期:2019-03-13 00:00:00

  • Epigenetics and aging.

    abstract::Over the past decade, a growing number of studies have revealed that progressive changes to epigenetic information accompany aging in both dividing and nondividing cells. Functional studies in model organisms and humans indicate that epigenetic changes have a huge influence on the aging process. These epigenetic chang...

    journal_title:Science advances

    pub_type: 杂志文章,评审

    doi:10.1126/sciadv.1600584

    authors: Pal S,Tyler JK

    更新日期:2016-07-29 00:00:00