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ACS Catalysis
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(1) (a) Gelalcha, F. G.; B. Bitterlich, G.; Anilkumar, M. K.; Tse, M.;
P=O of phosphoric acid due to the length of this bond is around
1.84-1.86 Å which can help substrate approach catalyst.
Comparing two transition states, TS I-re leads to a higher free
energy barrier than TS I-si by 5.5 kcal mol-1 as the result of
steric compulsion between tert-butyl of sulfenamide and 3,3’-
aromatic substituent of catalyst 4l (Figure 1). These calculated
results indicate that the (S)-products should be formed
preferentially, which is consistent with the experimental
observations. As a result, the activation and the transfer of
oxygen atom from H2O2 to sulfenamide was controlled by
phosphoric acid simultaneously so as to keep the
stereoselectivity of the product. Therefore, the methylated
sulfenamide could not be oxidized due to the missing of the
hydrogen bond (TS II). Meanwhile, to determine that the
catalytic action comes from phosphoric acid rather than Mg-
phosphate, chiral Mg-phosphate (4l)2Mg was prepared from 4l
and Mg(O-t-Bu)2. 21 However, the corresponding sulfinamide
was not formed even at room temperature, (eq. 3, Scheme 5).
Moreover, we found that the reaction yield and ee could be
improved and finally maintained after the addition of excess
anhydrous MgSO4, which might preclude the possibility that
water takes part in the transition state 20, (see supporting
information).
Beller, M. Iron-Catalyzed Asymmetric Epoxidation of Aromatic
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Murase, T.; Yanamoto, M.; Shiro, M. Asymmetric Catalytic
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Zang, C.; Liu,Y.; Xu, Z.-J.; Tse, C.; Guan, X.; Wei, J.; Huang, J.-S.
Highly Enantioselective Iron-Catalyzed cis-Dihydroxylation of
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a Non ‐ Heme Iron Catalyst: A Functional Model for Rieske
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In summary, we have developed an efficient method for
obtaining chiral sulfinamides through asymmetric oxidation of
sulfenamides with aqueous H2O2 as terminal oxidant. To the
best of our knowledge, this is unprecedented for preparation of
chiral sulfinamides due to the fact that they were prepared
indirectly through resolving, chiral reagent, or chiral auxiliaries
up to the present. Meanwhile, this procedure is more in line with
atomic economic benefits and green chemistry considering the
following advantages: environmentally benign aqueous H2O2
(35%) as the oxidant, organocatalysis, very clean reaction
without over-oxidation byproduct, high levels of yield (up to
96%) and enantioselectivity (up to 98%), easy workup, etc.
Moreover, the chiral sulfinamide obtained could be easily
derivatized to most of the chiral sulfoxides or other
sulfinamides in high yields and enantioselectivities.
ASSOCIATED CONTENT
Supporting Information.
Experimental procedures and compound characterization. This
material is available free of charge via the Internet at
AUTHOR INFORMATION
Corresponding Author
Acknowledgement.
We are grateful for financial support from the Youth Innovation
Promotion Association CAS (2018402); the Natural Science
Foundation of Sichuan province, China (2017JY0055); the
Innovative Team of Sichuan Province (grant numbers
2017TD0021, 2012SZ0219). The numerical calculations in this
paper have been done on the supercomputing system in the
Supercomputing Center of University of Science and Technology
of China.
(8) (a) Zhu, T.-S.; Jin, S.-S.; Xu, M.-H. Rhodium-Catalyzed, Highly
Enantioselective 1,2-Addition of Aryl Boronic Acids to α-Ketoesters
and α-Diketones Using Simple, Chiral Sulfur-Olefin Ligands. Angew.
Chem. Int. Ed. 2012, 51, 780-783. (b) Kimmel, K. L.; Weaver, J. D.;
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