Phosphine-Catalyzed [3+2] or [4+2] Cycloaddition/SN2 Substitution Domino Reaction of ortho-Aminotrifluoroaceto- phenone Derivatives with Hex-3-yn-2-one: Preparation of Functionalized 1-Benzazepine Compounds

Article abstract of DOI:10.1002/adsc.201700778

In this paper, we disclose a novel strategy for the phosphine-catalyzed cycloaddition/S_N2 substitution domino reaction, giving functionalized O-bridged benzoazepine and benzoxazepine derivatives in moderate to good yields. Changing the N–H protecting group of ortho-aminotrifluoroacetophenone derivatives gave different bridged-ring products in one step. (Figure presented.).

Full text of DOI:10.1002/adsc.201700778

Title: Phosphine Catalyzed [3+2] or [4+2] Cycloaddition/
SN2 Substitution Domino Reaction of ortho-Amino
Trifluoroacetophenone Derivatives with Hex-3-yn-2-one:
Preparation of Functionalized 1-Benzazepine Compounds
Authors: Min Shi, Yao-Liang Sun, and Yin Wei
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Adv. Synth. Catal. 10.1002/adsc.201700778
Link to VoR: http://dx.doi.org/10.1002/adsc.201700778

10.1002/adsc.201700778
Advanced Synthesis & Catalysis
.
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Phosphine Catalyzed [3+2] or [4+2] Cycloaddition/SN2 Substitution
Domino Reaction of ortho-Amino Trifluoroacetophenone Derivatives
with Hex-3-yn-2-one: Preparation of Functionalized 1-Benzazepine
Compounds
Yao-Liang Sun,a Yin Wei,b Min Shi*a,b,c
a
Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry & Molecular Engineering,
East China University of Science and Technology, 130 Mei Long Road, Shanghai 200237 China.
b State Key Laboratory and Institute of Elemento-organic Chemistry, Nankai university, Tianjin 300071, P. R. China.
c
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of
Sciences, 354 Fenglin Lu, Shanghai 200032 China.
Fax: (+86)-21-6416-6128; e-mail: mshi@mail.sioc.ac.cn
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
reported. Recently, our group has focused on the development of
alkynone chemistry upon phosphine catalysis and found that a
novel δ,β-zwitterionic intermediate A could be generated from the
addition of P(4-FC6H4)3 to ethyl alkynone,[14] which could
efficiently react with trifluoroacetyl compounds to afford δ-
addition products. Moreover, with the assistance of intramolecular
hydrogen bonding, cycloaddition of zwitterionic intermediate A
with trifluoroacetyl compounds was also possible upon phosphine
catalysis (Scheme 1, previous work).[15]
We envisaged that zwitterionic intermediate A could
undergo a cycloaddition/SN2 substitution domino process with an
additional nucleophile tethered with trifluoroacetyl compounds.
Herein, we wish to report the first example of cycloaddition/SN2
Abstract. In this paper, we disclosed a novel strategy for
the phosphine catalyzed cycloaddition/SN2 substitution
domino reaction, giving functionalized O-bridged
benzoazepine and benzoxazepine derivatives in moderate
to good yields. Changing the N-H protecting group of
ortho-amino trifluoroacetophenone derivatives gave
different bridged-ring products in one step.
Keywords: phosphine catalysis, alkyone, domino reaction,
bridged-ring compound.
Keywords: phosphine catalysis, alkyone, domino reaction,
bridged-ring compound.
substitution
domino
reaction
of
ortho-amino
trifluoroacetophenone derivatives with 3-hex-2-one to form two
kinds of CF3-containing[16] O-bridged benzoazepine[17] and
benzoxazepine derivatives[18] (Scheme 1, this work).
Introduction
Recently, nucleophilic phosphine organocatalysis[1] has made
remarkable and continuous progress due to its wide applicability
in the construction of carbo- and heterocyclic systems,[2] which
have potential applications for the synthesis of crucial moieties in
important drug leads.[3] On the basis of the pioneering work of
Lu,[4a, 4b, 2j, 4c, 4d] Kwon,[5] Huang[6] and Marinetti,[7] several novel
strategies on the phosphine catalyzed cycloadditions have been
established, that could be widely used in the synthesis of
functionalized nitrogen- and oxygen-containing heterocyclic
compounds.[8] Following these pioneering reports, complex
molecules such as fused aromatic rings,[9] polycyclic
compounds[10] and bridged-ring structures[11] could be directly and
efficiently constructed.
Alkynones can be activated by tertiary phosphine as a
nucleophilic catalyst to generate zwitterionic intermediates, which
can undergo nucleophilic additions[12] or annulations with other
10d]
electrophiles in different pathways.[13,
However, domino
annulations of alkynones with other electrophiles are scarcely
1
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10.1002/adsc.201700778
Advanced Synthesis & Catalysis
Scheme 1. Our strategies of phosphine catalyzed activation of
alkynones via vinyl phosphoniums.
investigated the substrate scope of the reaction with respect to
a
variety of 2-(2,2,2-trifluoroacetyl)phenylamides 1 with
different N-alkyl groups and the results are outlined in Table 2.
As can be seen, various N-benzyl group substituted 2-(2,2,2-
trifluoroacetyl)phenylamides 1b-1m afforded the desired
bridged-ring products 3b-3m in good to excellent yields
regardless of whether electron-withdrawing or -donating
substituent was introduced on the aromatic ring. Substrate 1i
bearing 2-bromobenzyl group afforded the corresponding
product 3i in 54% yield presumably due to the steric hindrance.
Replacing benzyl group by naphthalen-2-ylmethyl group (1l)
or thiophen-3-ylmethyl (1m) did not influence the yield
significantly, giving 3l in 76% yield and 3m in 73% yield,
respectively. As for substrate 1n, in which R1 = allyl, 3n was
isolated in 46% yield under the standard conditions similar as
N-benzyl derivatives. When R1 = Me or Et, the reaction
mixture became a mess under the standard conditions. The
desired products 3o and 3p were produced in 20% yield and
31% yield without using Na2CO3 as an additive. Probably, the
stronger basicity of N-alkyl group influences the SN2
substitution proceeding and Na2CO3 might accelerate the side
reactions. In addition, N-Me and N-Et products were found to
be unstable at high temperature.
Results and discussion
Our
study
commenced
with
1-(5-chloro-2-((4-
1a
methylbenzyl)amino)phenyl)-2,2,2-trifluoroethan-1-one
and hex-3-yn-2-one 2a as the substrates in the presence of
PPh3 (20 mol%) in toluene (1.0 mL) at room temperature,
affording the desired product 3a in 14% yield after 72 hours
(Table 1, entry 1). Other phosphine catalysts also gave 3a in
low yields along with recovery of 1a (Table 1, entries 2-3).
Raising the reaction temperature to 65 oC gave 3a in 26%
yield if using PPh3 (20 mol%) as the catalyst (Table 1, entry 4).
o
Moreover, 3a could be produced in 40% yield at 65 C when
P(4-FC6H4)3 (20 mol%) was employed (Table 1, entry 5). The
examination of solvent effect revealed that toluene and
dioxane were the suitable media (Table 1, entries 6-13). Next,
we examined a variety of additives such as phenol, benzoic
acid, water and HFIP (1,1,1,3,3,3-hexafluoro-2-propanol) and
identified that none of these additives benefited the reaction
proceeding (Table 1, entries 10-16). Organic bases could not
improve the reaction yields (Table 1, entries 18-22). Using
inorganic bases as additives could improve the yield of 3a and
addition of Na2CO3 (1.0 equiv) could afford 3a in 73% NMR
Table 2. Reaction Scope: O-bridged benzoazepine derivatives
3.[a][b]
o
yield (72% isolated yield) in toluene at 65 C (Table 1, entries
23-24). In the absence of phosphine, no reaction occurred
(Table 1, entry 25). Thus, the best reaction conditions are
using P(4-FC6H4)3 (20 mol%) as the catalyst, Na2CO3 (1.0
equiv) as the additive and carrying out the reaction in toluene
at 65 oC for 72 hours (see Table S1 in the Supporting
Information for the more details).
Table 1. Optimization of the reaction conditions for the synthesis
of 3a.
Next, the substituents on the benzene ring of 1 were also
examined with substrates 1q-1y as shown in Table 3. If
without substituent on the benzene ring or substrates
containing electron-deficient aromatic ring, the reactions
proceeded smoothly to give the corresponding bicyclic
products 3q-3v in 65-85% yields. Substrates 1w-1y containing
electron-donating groups such as OMe, Me and i-Pr groups
afforded the corresponding products in moderate yields (33%-
65%), suggesting that electron-donating group on the benzene
ring would impair the reaction proceeding. Next, the
substituent in acyl group was tested. When R = CF2Cl, the
desired product 3z was obtained in 53% yield. However, using
CF2CF3 instead of CF3 failed to give the desired product 3aa.
When R = Me or Ph, no reaction occurred, suggesting that
trifluoromethyl group activated acyl group is essential for the
reaction
with
zwitterionic
intermediate
A.
(Z)-4-
(benzylamino)-1,1,1-trifluorobut-3-en-2-one 1ad also failed to
Having the optimal reaction conditions in hand, we next
2
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10.1002/adsc.201700778
Advanced Synthesis & Catalysis
afford the desired product 3ad. Attempts to synthesize ortho-
aminobenzoyl formats met with little success; replacement of
CF3 with CO2R or CN groups made compound 1 unstable and
was converted to isatin in situ.
Table 3. Reaction Scope: Synthesis of O-bridged benzoazepine
derivatives 3.[a][b]
Scheme 3. Synthesis of polycyclic product 5.
The derivatizations of these functionalized O-bridged
benzoazepine and benzoxazepine derivatives were performed
as shown in Scheme 4. Treatment of 3a with NaBH4 provided
6 in 99% yield (7:1 dr), which could be transformed into 7 as a
single diastereoisomer in 55% yield via Mitsunobu reaction
(Scheme 4, eq. 1). In this case, another diastereoisomer was
only isolated in trace. Similarly, phthalimide substituted
product 8 was obtained in 24% yield from 5a’ as a single
diastereoisomer after two steps (Scheme 4, eq. 2). The
structures of 7 and 8 have been unambiguously assigned by X-
ray diffraction and their ORTEP drawings are shown in Figure
1 and the CIF data are summarized in the Supporting
Information. The asymmetric variant of 1a and 2a has been
attempted using several chiral phosphines as catalysts, but no
satisfactory results were achieved, presumably due to that the
chiral phosphine center is far away from the reaction site (see
Table S2 in the Supporting Information). Using (S)-DTBM-
SegPhos (20 mol%) as the catalyst afforded 3a in 75% yield
along with 40% ee value (Scheme 4, eq. 3).
Subsequently, we turned our attention to substrate scope
with respect to the alkynones. As shown in Scheme 2, the use
of 1-phenylpent-2-yn-1-one 2b instead of 2a did not afford the
desired product (Scheme 2, eq. 1). When the δ-position of hex-
3-yn-2-one 1a was substituted by a phenyl group, no reaction
occurred (Scheme 2, eq. 2). These results suggested that the
steric effect in both α’-position and δ-position could
significantly influence the generation of key zwitterionic
intermediate A and defer the reaction proceeding.
Scheme 2. The substituent effect of alkynones.
As compared with N-alkyl substrates 1, sulfonated
substrates 4 produced different bridged-ring compounds. For
example, tosylated substrate 4a gave 5a and 5a’ as a pair of
diastereoisomers in 80% total yield under the standard
conditions (Scheme 3). For substrate 4b bearing a para-
bromobenzenesulfonyl group, 5b was given in 54% yield (2:1
dr). However, in the case of substrate 4c, the desired product
5c were only isolated in 32% yield as a single diastereoisomer
in the absence of Na2CO3. In our unpublished results, a
considerable amount of N-acyl substrates were also examined,
but only the corresponding cycloaddition products were isolated
without domino reaction took place under the standard conditions.
The more acidic N-H group of N-sulfonated substrates 4 plays
Scheme 4. Derivatization and asymmetric variant
a
key role in the production of different bridged-ring
compounds (see Scheme 6).
3
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10.1002/adsc.201700778
Advanced Synthesis & Catalysis
tertiary phosphine to the β-carbon of hex-3-yn-2-one 2a.
Intermediate A can attack trifluoroacetyl group of 1a to afford
vinyl phosphonium species B. As aforementioned, N-H
moieties of N-sulfonated substrates 4 are more acidic than
those of N-benzyl substrates 1,[19] the proton abstraction of N-
H moieties of N-benzyl substrates 1 should be more difficult
than those of N-sulfonated substrates 4. The different pKa
values between sulfoamides and amines changed the sequence
of proton migration, leading to divergent reaction pathways.
When the N-protecting group is an alkyl group, oxygen anion
of intermediate B prefers to abstract the proton of more acidic
carbonyl’s α site rather than the proton of amino group, giving
zwitterionic intermediate C. Zwitterionic intermediate
abstracts the proton of hydroxyl group again to afford
intermediate D. Cyclization of intermediate provides
C
D
intermediate E. The proton shift takes place again to deliver
intermediate F, which undergoes SN2 substitution to furnish
product 3a and the phosphine catalyst. When the N-protecting
group is a sulfonyl group, the oxygen anion of intermediate B
directly abstracts the proton of N-H group to give intermediate
G, which undergoes cyclization to give intermediate H. This
intermediate
abstraction, which produces 5a through
H
produces intermediate
I
via
a
a
proton
subsequent
intramolecular SN2 substitution. Previously, Huang and co-
workers reported a PPh3 catalyzed aza-MBH/aza-Michael
domino reaction between salicyl N-tosylimines and allenoates.
Unlike Huang’s work, we did not detect any product H' during
the reaction, suggesting that this domino process may not
proceed via a stepwise pathway.
Figure 1. X-ray crystal structures of products 7 and 8.
Scheme 6. A plausible reaction mechanism.
To clarify the reaction mechanism, two deuterium-
labeling experiments were conducted under the standard
conditions. The reaction of 1a with 2a was first carried out in
the presence of D2O (10 equiv) under the standard reaction
conditions. The reaction proceeded smoothly to give the
corresponding partially deuterated product [D]-3a in 63%
yield along with the deuterium incorporation at C1~C4
positions (Scheme 5, eq. 1), suggesting the generation of these
carbon anionic sites during the catalytic cycle. Using 80%
deuterated [D]-1a as substrate produced no deuterium
incorporated product 3a in 67% yield, probably due to the
scrambling by excess amounts of alkynone 2a in toluene
(Scheme 5, eq. 2).
Conclusion
Scheme 5. Deuterium-labeling experiments
In conclusion, a novel phosphine catalyzed cycloaddition/SN2
substitution domino reaction to synthesize substituted
functionalized O-bridged benzoazepine and benzoxazepine
derivatives has been developed for the first time. Among these
domino processes, the [3+2] or [4+2] annulation in the first step
can be simply adjusted by changing the intramolecular N-H
According to the above experimental results and pervious
reports,
a plausible reaction mechanism for phosphine
catalyzed cycloaddition/SN2 substitution domino process has
been outlined in Scheme 6. The reaction is initiated with the in
situ generated zwitterion A derived from the addition of
4
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10.1002/adsc.201700778
Advanced Synthesis & Catalysis
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Experimental Section
General Procedure for Synthesis of 3
A Schlenk tube was heated under vacuum to remove ambient
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o
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Acknowledgements
We are grateful for the financial support from the National Basic
Research Program of China (973)-2015CB856603, the Strategic
Priority Research Program of the Chinese Academy of Sciences,
Grant No. XDB20000000, the National Natural Science
Foundation of China (20472096, 21372241, 21572052, 20672127,
21421091, 21372250, 21121062, 21302203, and 20732008), and
the Fundamental Research Funds for the Central Universities
222201717003.
5
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10.1002/adsc.201700778
Advanced Synthesis & Catalysis
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[19] In general, sulfoamides have smaller pKa values than amines. See:
Bordwell
pKa
values
on
http://www.chem.wisc.edu/areas/reich/pkatable/index.htm
references therein.
and
6
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10.1002/adsc.201700778
Advanced Synthesis & Catalysis
FULL PAPER
Phosphine
Catalyzed
[3+2]
or
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Cycloaddition/SN2 Substitution Domino Reaction of
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Adv. Synth. Catal. Year, Volume, Page – Page
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7
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