Synthesis of oxazine-embedded 1,1′-biaryl-2,2′-diamine via [3,3]-sigmatropic rearrangement of oxazine diarylhydrazine

Full text of DOI:10.1002/bkcs.10871

Communication
DOI: 10.1002/bkcs.10871
BULLETIN OF THE
B.-Y. Lim et al.
KOREAN CHEMICAL SOCIETY
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Synthesis of Oxazine-Embedded 1,1 -Biaryl-2,2 -diamine via [3,3]-
Sigmatropic Rearrangement of Oxazine Diarylhydrazine
*
Byeong-Yun Lim, Chang-Heon Suhl, and Cheon-Gyu Cho
Department of Chemistry, Hanyang University, Seoul 04763, Korea. *E-mail: ccho@hanyang.ac.kr
Received June 15, 2016, Accepted June 23, 2016, Published online July 31, 2016
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Keywords: [3,3]-Sigmatropic rearrangement, Benzidine rearrangement, 1,1 -Biaryl-2,2 -diamines
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Axially chiral 1,1 -binaphthyl-2,2 -diamine (BINAM) and its
reduction of the lactam carbonyl group was achieved with
1
derivatives are important chiral ligands and organocatalysts
proven to be effective in various asymmetric transformations
LiAlH on heating in tetrahydrofuran (THF) under reflux to
4
7
provide diarylhydrazine 2a.
2
a,b
2e
2c
2f
including
epoxide
opening,
hydrogenation,
The [3,3]-sigmatropic rearrangement of diarylhydrazine
2a was investigated under various reaction conditions
(Table 1). In these experiments, the reactions were carried
out in a dilute premixed acid solution. When stirred in
EtOH with 1.2 equiv HCl at room temperature, the reaction
gave diamine 1a in 71% yield (entry 1). Lowering the reac-
2
d
hydroamination, carbosulfenylation, conjugate addition,
2g
2h
domino-Michael–aldol, and Diels–Alder reaction . As with
BINOL (1,1 -bi-2-naphthol) or BINAP (2,2 -bis(diphenylpho-
0
0
0
0
sphino)-1,1 -binaphthalene), bulky aryl substituents at 3,3 -
positions of BINAM proved to enhance stereoselectivity. Lit-
erature survey revealed only a few synthetic methods, most
of which rely on a directed ortho-lithiation/halogenation fol-
lowed by Pd-catalyzed coupling or a Pd-catalyzed direct
ꢀ
tion temperature to 0 C gave much cleaner reactions
(entries 2 and 3). With 1.2 equiv of HCl, the reaction gave
8
3
3% yield after 12 h. The reaction time was shortened to
0 min with a slightly higher product yield of 89% in the
2
c,d,3
C H arylation, among other less efficient ones.
How-
presence of excess HCl (20 equiv). Use of a weaker acid
resulted in slower reaction (entry 4).
ever, installation of the bulky aryl groups is by no means
straightforward and often requires hazardous reagents, harsh
reaction conditions, or low yielding lengthy steps. Such diffi-
culties together with lack of a reliable method to the BINAM
core hamper further development of BINAM-derived chiral
ligands and organocatalysts. As a part of our ongoing study
With optimal reaction conditions in hand, various other
oxazine diarylhydrazines were prepared. Iodobenzene with
electron-withdrawing substituent was not considered
because of potential incompatibility with the ensuing
LiAlH4 reduction conditions (Table 2). When subjected
into the conditions used for 8a, hydrazide 6 gave oxazine
diaryl hydrazides 8b–8f mostly in good yield. The resulting
diaryl hydrazides were then reduced to set the stage for the
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on aryl hydrazides, we have envisioned the oxazine unit
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0
incorporated in the 1,1 -biaryl-2,2 -diamines 2 could provide
the required steric bias for effective stereocontrol. Prompted
by their potentials as new chiral ligands and organocatalysts,
we set out to investigate the synthesis of oxazine-embedded
[3,3]-sigmatropic rearrangement reactions. In all cases
0 0
,1 -biaryl-2,2 -diamine 2 by using [3,3]-sigmatropic rear-
rangement of diarylhydrazines 1 (Scheme 1).
except 8e (21% for the reduction to 2e, entry 4), the reduc-
1
4d,k,5
tion and rearrangement reactions well proceeded to give
0 0
,1 -biaryl-2,2 -diamines 1b–1f in good overall yields.
1
The present study was commenced by the preparation of
diarylhydrazine 2a from 2-iodo-3-methoxy-naphthalene (3)
6
(
Scheme 2). BBr -mediated demethylation followed by the
3
reaction with ethyl chloroacetate furnished acetate 4, which
on gentle heating with hydrazine hydrate yielded aryl
hydrazide 5 in good overall yield. Intramolecular Cu-
catalyzed C N coupling reaction gave cyclic hydrazide
6
in 79% yield. The C N coupling reaction with iodoben-
zene afforded diaryl hydrazide 8a in 65% yield. The
3
Scheme 2. Reaction conditions: (a) BBr , methylene chloride, room
temperature, overnight, 91%; (b) ClCH CO
maldehyde, 115 C, 2 h, 99%; (c) hydrazine hydrate, MeOH, 40 C,
2
2
Et, K
2
CO
3
, dimethylfor-
ꢀ
ꢀ
ꢀ
2
4 h, 90%; (d) CuI, 1,10-phenanthroline, Cs
2
CO
3
, DMF, 80 C, 2 h,
7
9%; (e) iodobenzene, Pd(OAc)
2
, [(tBu)
3
P]HBF
4
2 3
, Cs CO , tol,
ꢀ
0
0
110 C, 24 h, 65%; (f ) LiAlH , THF, reflux, 24 h, 89%.
Scheme 1. Synthetic plan to 1,1 -biaryl-2,2 -diamine.
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Bull. Korean Chem. Soc. 2016, Vol. 37, 1171–1172
© 2016 Korean Chemical Society, Seoul & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Wiley Online Library 1171

Communication
ISSN (Print) 0253-2964 | (Online) 1229-5949
BULLETIN OF THE
KOREAN CHEMICAL SOCIETY
Table 1. Model study under various conditions.
with LiAlH in THF under reflux implemented both reduc-
4
tion and [3,3]-sigmatropic rearrangement to directly provide
BINAM derivative 13 in 72% total yield.
In summary, diarylhydrazine with oxazine unit(s) under-
goes [3,3]-sigmatropic rearrangement to give novel
0
0
oxazine-embedded 1,1 -biaryl-2,2 -diamine in good yield.
Acknowledgments. This work was supported by the
grants from the NRF Korea (2012M3A7B4049657).
Entry Acid (equiv) Conditions
Yield (%)
References
1
2
3
4
HCl (1.2)
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71
83
89
ꢀ
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PH] BF4, Cs
2
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4
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ꢀ
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(
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1
-yl)uranium tetrafluoroborate, 2,6-lutidine, 5, DCM, room tem-
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2
3
ꢀ ꢀ
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4
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8
2
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1
6
this, ester 4 was hydrolyzed to acid 9 for the coupling with
hydrazide 5 to afford diaryl hydrazide 10. Subsequent
C N coupling reaction gave 11 in 93% yield. Reaction
7. No rearrangement was observed with diaryl hydrazide 8a.
Bull. Korean Chem. Soc. 2016, Vol. 37, 1171–1172
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