10.1002/adsc.201801670
Advanced Synthesis & Catalysis
Kojima, S. Minakata, Angew. Chem. Int. Ed. 2015, 54,
[9] 2u can also be produced efficiently via deprotection of
the PMP group of 2c. For details, see Supporting
Information.
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amine 1a, which gives only trace amount of rearranged
aldehyde product (most of the start material was
recovered and the by-product is PhNHEt).
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[13] For details, see Supporting Information 6.5.
[14] No rearrangement product was detected when the
reaction was carried out in the presence of 1 equiv of a
hypervalent iodine reagent such as NIS, PhI(OAc)2, or
2-iodoxybenzoic acid. Only trace amount of product
was detected when a mixture of one equivalent of I2
and two equivalent of KOH was employed.
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of intermediate 12 involving a C-N bond cleavage is
possible. For cyclic amines, the intermediate 12 can be
regenerated easily from the de-composed byprodut.
However, for acyclic amines, the decomposition of the
intermediate 12 became the major side reaction. This
can partially interpret why we used alcohol for acyclic
amines and H2O for cyclic amines.
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[8] For details about optimization of reaction conditions
such as solvents, additives and temperatures, see
Supporting Information, Table S1.
5
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