Asymmetric abstraction of two chemically-equivalent methylene hydrogens: significant enantioselectivity of endoperoxide presented by fumitremorgin B endoperoxidase
Literature Information
Jian-Nan Ji, Shi-Lu Chen
The combination of the inert C–H bond activation and asymmetric synthesis, especially the transformation of prochiral sp3 precursors to chiral sp3 centers, is a profound challenge. In the present DFT calculations, the unique enantioselectivity in verruculogen biosynthesis catalyzed by fumitremorgin B endoperoxidase (FtmOx1) has been mechanistically investigated, where a prochiral methylene in fumitremorgin B is dominantly converted to an R-chiral eight-membered endoperoxy ring. FtmOx1 is the first-reported mononuclear α-ketoglutarate-dependent non-heme iron enzyme responsible for chiral endoperoxide formation, which handles the substrate using a Tyr224 radical resulting from the hydrogen abstraction by an FeIVO species. It is demonstrated that the perfect enantioselectivity of the R-endoperoxy ring originates from the asymmetric abstraction of two chemically-equivalent methylene hydrogens from substrate chain A by the Tyr224 radical and the high conformation stability of the resultant chain A radical due to steric effects. The barrier difference in the abstraction of two hydrogens is 5.6 kcal mol−1. The hydrogen abstraction by the Tyr224 radical is rate-limiting in the FtmOx1 reaction with an overall barrier of 18.6 kcal mol−1. The results obtained here advance the understanding of the chemistry in enantioselectivity, providing a potentially general way for the transformation of prochiral sp3 precursors to chiral sp3 centers.
Related Literature
Microwave-assisted synthesis of near-infrared fluorescent sphingosine derivatives
Kumar R. Bhushan, Fangbing Liu, Preeti Misra, John V. Frangioni
DOI: 10.1039/B807930G
Controlled formation of porous magnetic nanorodsvia a liquid/liquid solvothermal method
Oscar Bomati-Miguel, Aldo F. Rebolledo, Pedro Tartaj
DOI: 10.1039/B805239E
Spontaneous formation of a chiral supramolecular superhelix in the crystalline state using a single-stranded tetranuclear metallohelicate
Shigehisa Akine, Takashi Matsumoto, Tatsuya Nabeshima
DOI: 10.1039/B810426C
Direct functionalization at the boron center of antiaromatic chloroborole
Holger Braunschweig, Thomas Kupfer
DOI: 10.1039/B808483A
An electrochemical sensor for 3,4-dihydroxyphenylacetic acid with carbon nanotubes as electronic transducer and synthetic cyclophane as recognition element
Jie Yan, Yucheng Zhou, Ping Yu, Lei Su, Lanqun Mao, Deqing Zhang, Daoben Zhu
DOI: 10.1039/B805958F
Microwave effect on the surface composition of the Urushibara Ni hydrogenation catalyst and improved reduction of acetophenone
Junichi Tsuzuki, Futoshi Sakai, Masatsugu Kajitani, Nick Serpone
DOI: 10.1039/B808188C
Is catenation beneficial for hydrogenstorage in metal–organic frameworks?
Patrick Ryan, Linda J. Broadbelt, Randall Q. Snurr
DOI: 10.1039/B804343D
Oxidative decarboxylative synthesis of 2-H-imidazolines from glyoxylic acid and 1,2-diamines
Kenichi Murai, Maiko Morishita, Ryo Nakatani, Hiromichi Fujioka, Yasuyuki Kita
DOI: 10.1039/B807810F
Cyclometallated platinum(ii) complexes incorporating ethynyl–flavoneligands: switching between triplet and singlet emission induced by selective binding of Pb2+ ions
Pierre-Henri Lanoë, Jean-Luc Fillaut, Loïc Toupet, J. A. Gareth Williams, Hubert Le Bozec, Véronique Guerchais
DOI: 10.1039/B806935B
Fine control over the morphology and structure of mesoporous silica nanomaterials by a dual-templating approach
Junhui He
DOI: 10.1039/B807787H
You might also like
What precautions should be taken when handling 4-(2-Furylmethyl)thiomorpholine 1,1-dioxide (CAS: 79206-94-3)?
When handling 4-(2-Furylmethyl)thiomorpholine 1,1-dioxide (CAS: 79206-94-3), it ...
What precautions should be taken when handling 4-Chloro-N-[2-(4-morpholinyl)ethyl]benzamide (CAS: 71320-77-9)?
When handling 4-Chloro-N-[2-(4-morpholinyl)ethyl]benzamide (CAS: 71320-77-9), it...
How should waste containing 2-[2-(2-Methoxyethoxy)ethoxy]ethyl 4-methylbenzenesulfonate (CAS: 62921-74-8) be handled?
Waste containing this compound (CAS: 62921-74-8) should be handled according to ...
How should waste containing (S)-Methyl 2-amino-3-cyclohexylpropanoate be handled?
Waste containing (S)-Methyl 2-amino-3-cyclohexylpropanoate should be collected i...
How is 5-({4-[(2S,4R)-4-Hydroxy-2-methyltetrahydro-2H-pyran-4-yl]-2-thienyl}sulfanyl)-1-methyl-1,3-dihydro-2H-indol-2-one (CAS: 166882-70-8) typically synthesized?
This compound can be synthesized using a multi-step process involving the conjug...
Are there alternatives to (2E)-3-(3,4-Dichlorophenyl)acrylic acid (CAS: 7312-27-8) in synthesis?
There are several alternatives to (2E)-3-(3,4-Dichlorophenyl)acrylic acid in syn...
How should Ethyl 6-(2-nitrophenyl)imidazo[2,1-b][1,3]thiazole-3-carboxylate (CAS: 925437-84-9) be stored?
Ethyl 6-(2-nitrophenyl)imidazo[2,1-b][1,3]thiazole-3-carboxylate (CAS: 925437-84...
How should waste containing 2-(1,3-Thiazol-2-yl)ethanamine (CAS: 18453-07-1) be handled?
Waste containing 2-(1,3-Thiazol-2-yl)ethanamine (CAS: 18453-07-1) should be coll...
How is Methyl 5-iodo-2-methylbenzoate (CAS: 103440-54-6) typically synthesized?
Methyl 5-iodo-2-methylbenzoate can be synthesized through the iodination of meth...
How is 5-Chloro[1,2,4]triazolo[1,5-a]pyridine (CAS: 1427399-34-5) typically synthesized?
5-Chloro[1,2,4]triazolo[1,5-a]pyridine is commonly synthesized via the condensat...
Source Journal
Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.














