Organic Letters
Letter
Bo Tang − College of Chemistry, Chemical Engineering and
Materials Science, Collaborative Innovation Center of
Functionalized Probes for Chemical Imaging in Universities of
Shandong, Key Laboratory of Molecular and Nano Probes,
Ministry of Education, Shandong Provincial Key Laboratory of
Clean Production of Fine Chemicals, Shandong Normal
Scheme 6. Deuterated Product Derivatizations
Authors
Li Zhang − College of Chemistry, Chemical Engineering and
Materials Science, Collaborative Innovation Center of
Functionalized Probes for Chemical Imaging in Universities of
Shandong, Key Laboratory of Molecular and Nano Probes,
Ministry of Education, Shandong Provincial Key Laboratory of
Clean Production of Fine Chemicals, Shandong Normal
University, Jinan 250014, P. R. China
Kaiyue Fu − College of Chemistry, Chemical Engineering and
Materials Science, Collaborative Innovation Center of
Functionalized Probes for Chemical Imaging in Universities of
Shandong, Key Laboratory of Molecular and Nano Probes,
Ministry of Education, Shandong Provincial Key Laboratory of
Clean Production of Fine Chemicals, Shandong Normal
University, Jinan 250014, P. R. China
Yaxin Sun − College of Chemistry, Chemical Engineering and
Materials Science, Collaborative Innovation Center of
Functionalized Probes for Chemical Imaging in Universities of
Shandong, Key Laboratory of Molecular and Nano Probes,
Ministry of Education, Shandong Provincial Key Laboratory of
Clean Production of Fine Chemicals, Shandong Normal
University, Jinan 250014, P. R. China
Xiuhua Wang − College of Chemistry, Chemical Engineering and
Materials Science, Collaborative Innovation Center of
Functionalized Probes for Chemical Imaging in Universities of
Shandong, Key Laboratory of Molecular and Nano Probes,
Ministry of Education, Shandong Provincial Key Laboratory of
Clean Production of Fine Chemicals, Shandong Normal
University, Jinan 250014, P. R. China
molecular oxidative coupling, resulting in optically pure biaryl
sultams 10 in 52% yield with 97% ee and 98% deuterium
content (Scheme 6b).26 The sulfonyl group could be removed
to afford α-deuterated chiral amine, which could be further
transformed to several chiral pharmaceuticals and bioactive
compounds.3
In summary, we have developed a nickel-catalyzed
enantioselective transfer hydrogenation of imines for the
synthesis of a wide variety of chiral sulfonamides. By using
cheap and harmless 2-propanol-d8 as the deuterium source, we
realized the α-selective deuteration of N-tosyl imines,
producing α-deuterated chiral amines with excellent deuterium
contents and enantioselectivity. Mechanism studies revealed
that the reaction may go through a stepwise pathway with
[Ni−D] as the key intermediate.
ASSOCIATED CONTENT
* Supporting Information
■
sı
The Supporting Information is available free of charge at
Experimental details and spectral characteristics of
Accession Codes
tallographic data for this paper. These data can be obtained
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
Jieyu Yue − College of Chemistry, Chemical Engineering and
Materials Science, Collaborative Innovation Center of
Functionalized Probes for Chemical Imaging in Universities of
Shandong, Key Laboratory of Molecular and Nano Probes,
Ministry of Education, Shandong Provincial Key Laboratory of
Clean Production of Fine Chemicals, Shandong Normal
University, Jinan 250014, P. R. China
AUTHOR INFORMATION
■
Complete contact information is available at:
Corresponding Authors
Peng Yang − College of Chemistry, Chemical Engineering and
Materials Science, Collaborative Innovation Center of
Functionalized Probes for Chemical Imaging in Universities of
Shandong, Key Laboratory of Molecular and Nano Probes,
Ministry of Education, Shandong Provincial Key Laboratory of
Clean Production of Fine Chemicals, Shandong Normal
Yu Ma − College of Chemistry, Chemical Engineering and
Materials Science, Collaborative Innovation Center of
Functionalized Probes for Chemical Imaging in Universities of
Shandong, Key Laboratory of Molecular and Nano Probes,
Ministry of Education, Shandong Provincial Key Laboratory of
Clean Production of Fine Chemicals, Shandong Normal
University, Jinan 250014, P. R. China; Email: may@
Author Contributions
†P.Y. and L.Z. contributed equally.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We thank the National Natural Science Foundation of China
(21602126, 91753111, 21675103, and 21804081), the Key
Research and Development Program of Shandong Province
(2018YFJH0502), and the Higher Educational Science and
Technology Program of Shandong Province (J18KA077) for
financial support.
E
Org. Lett. XXXX, XXX, XXX−XXX