Journal of the American Chemical Society
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Allan, K. M.; Stoltz, B. M. J. Am. Chem. Soc. 2008, 130, 17270-17271; h)
compound 8 with a N-Ms group reacted with 1b under our stand-
ard conditions, indoline 9 was obtained after hydrogenation,
showing that Ms can act as an effective group on substrates with
aliphatic amine, whereas there was no reaction at all when Ms
group was employed on aniline-based substrate. Selective amide
hydrolysis of compound 9 could be realized using DIBAL-H in
DCM at -78oC, and compound 10 was afforded in 84% yield.17
After connection with side-chain 11 using literature procedure,11a
Ibutamoren mesylate could be successfully prepared.
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In conclusion, an efficient, transition-metal-free, and broad-
spectrum domino aryne annulation approach through nucleo-
philic-ene cascade process was successfully developed, which
could construct various benzofused N-heterocycles and generate
substituted arenes in stereospecific manner. An essential factor for
the success of this domino transformation is to alter the leaving
ability of the second LG on 1,2-benzdiyne equivalents. This study
not only broadens the chemistry of 1,2-benzdiyne equivalents, but
also brings new aryne annulation avenue. Our ongoing work in-
cludes the in-depth mechanistic study of this process as well as
the development of more synthetic applications.
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ASSOCIATED CONTENT
Supporting Information. Experimental details for all chemical
reactions and measurements and X-ray single crystallographic
data. This material is available free of charge via the Internet at
AUTHOR INFORMATION
Corresponding Author
Author Contributions
†Xu, H. and He, J. contributed equally to this work.
Notes
The authors declare no competing financial interest.
(9) da Silva, V. B. R.; Campos, B. R. K. L.; de Oliveira, J. F.; Decout,
J.-L.; de Lima, M. D. C. A. Bioorg. Med. Chem. 2017, 25, 3259-3277.
(10) Creasey, W. A., The Monoterpenoid Indole Alkaloids. In the
Chemistry of Heterocyclic Compounds; Indole Series; Saxton, J. E., Ed.;
John Wiley and Sons: New York, 1983; Vol. 25.
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WO9818815A1, 1998; b) Smith, R. G. Endocr. Rev. 2005, 26, 346-360.
(12) The reaction of Kobayashi benzyne precursor with excess of both
Ts-protected aniline and cyclohexene afforded solely nucleophilic attack
product in 69% isolated yield, whereas there was no observation of any
intermolecular ene reaction product with cyclohexene:
ACKNOWLEDGMENT
The authors gratefully acknowledge research support of this work
by NSFC (21372268, 21772017) and Fundamental Research
Funds for the Central Universities (106112016CDJZR228806).
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