Cobalt-Catalyzed Diastereoselective [4+2] Annulation of Phosphinamides with Heterobicyclic Alkenes at Room Temperature

Article abstract of DOI:10.1002/adsc.201701162

Cobalt-catalyzed sp² C?H bond functionalization of diarylphosphinamides with heterobicyclic alkenes was demonstrated at room temperature employing commercially available cobalt(II)-salts. The effectiveness of this strategy was illustrated with the reaction of various 8-aminoquinoline derived phosphinic amides and 7-oxa/azabenzonorbornadienes. The reaction conditions exhibited excellent functional group tolerance and high diastereoselectivities. Furthermore, extension of this approach to the preparation of polyaryl cyclic phosphinamides was achieved through the dehydrative ring opening/aromatization sequence. (Figure presented.).

Full text of DOI:10.1002/adsc.201701162

Title: Cobalt-Catalyzed Diastereoselective [4+2] Annulation of
Phosphinamides with Heterobicyclic Alkenes at Room
Temperature
Authors: Chandra Mouleeswara Rao Volla, Rajender Nallagonda, and
Thrimurtulu Neetipalli
This manuscript has been accepted after peer review and appears as an
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content of this Accepted Article.
To be cited as: Adv. Synth. Catal. 10.1002/adsc.201701162
Link to VoR: http://dx.doi.org/10.1002/adsc.201701162

10.1002/adsc.201701162
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Cobalt-Catalyzed Diastereoselective [4+2] Annulation of
Phosphinamides with Heterobicyclic Alkenes at Room
Temperature
Rajender Nallagonda, Neetipalli Thrimurtulu and Chandra M. R. Volla*
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai-400076, India
Phone: +91-2225767188, Fax: +91-2225767152, email: Chandra.volla@chem.iitb.ac.in
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######.
sp2
diarylphosphinamides
C−H
bond
directed C-H activation of phosphorous derivatives
with would offer a straightforward method for accessing
Abstract:
functionalization
Cobalt-catalyzed
of
heterobicyclic alkenes was demonstrated at room
temperature employing commercially available cobalt (II)-
salts. The effectiveness of this strategy was illustrated with
the reaction of various 8-aminoquinoline derived
phosphinic amides and 7-oxa/azabenzonorbornadienes. The
reaction conditions exhibited excellent functional group
tolerance and high diastereoselectivities. Furthermore,
extension of this approach to the preparation of polyaryl
cyclic phosphinamides was achieved through the
dehydrative ring opening/aromatization sequence.
these privileged skeletons. Recently this synthetic
strategy gained much interest and was studied
employing expensive second row transition-metals.
Extensive work using P=O and P=S groups as
directing groups in C-H activation for preparing a
variety of heterocycles was reported by Lee, Kim,
Miura and others.[9-11] However, development of
novel
synthetic
methods
for
constructing
phosphaheterocycles employing earth-abundant first-
row transition-metal catalysts is highly desirable.
Furthermore, most of the transformations focussed on
ortho-functionalization and in comparison annulation
methods are much less explored. Aminoquinoline-
directed C-H activation of arylphosphinic amides
with 20 mol% of Co(NO3)2 was described by
Daugulis for the coupling of aryl sp2 C-H bonds with
alkynes.[12]
Keywords: C-H activation; Cobalt; [4+2] Annulation;
phosphinic amides; bicycloalkenes.
Transition-metal-catalyzed directed C-H bond
functionalization reactions have emerged as a
powerful technique in recent years for constructing
complex organic structures.[1] Great progress was
made in this area by employing precious noble-metal
catalysts like Pd, Rh, Ru and Ir. However, there is a
strong urge in the last few years to study alternative,
more economical and earth-abundant base-metal
catalysts.[2] In particular, cobalt-based catalysts have
been actively pursued for promoting a variety of sp2
and sp3 C-H functionalization reactions because of
their versatility and unique reactivity.[3] A number of
low-valent Co-catalyzed reactions were developed by
Yoshikai and co-workers.[4] C-H functionalization
reactions using Cp*Co(III)-catalysts were first
introduced by Matsunaga and Kanai in 2013.[5] In
contrast, bidentate chelating assisted C-H activation
reactions with commercially available Co(II)-salts
were demonstrated by Daugulis in 2014.[6] Later,
substantial contributions in Co(II)/Co(III)-catalyzed
C-H functionalization also came from many other
groups.[7]
Previous work :
(a) Naphthylation: Li, Miura and Cheng
O
DG
DG
H
Rh(III) or Co(III)
-H2O
+
(b) Hydroarylation: Bolm
DG
O
O
DG
+
Rh(III) or Ru(II)
H
(c) [3+2] Annulation: Cheng
O
O
H
O
O
Q
N
Co(II)
Ag(I) oxidant
+
H
H
H
(d) Present work: [4+2] Annulation
O
R
O
R
P
Q
H
O
R
N
X
P
Q
N
P
Q
Co(II)
Mn(III)
H
N
H
+
H
-H2O
X
H
X = O, N-PG
•
Aryl C-H activation
•
•
•
•
Room temperature
Excellent diastereoselectivity
Good functional group tolerance
On the other hand, organophosphorous derivatives
are important chemical entities and are widely
utilized in pharmaceuticals, agrochemicals, as ligands
for metal-catalysis, organocatalysts, as well as
advanced functional materials.[8] Metal-catalyzed
Q =
N
Scheme 1. Overview of the work.
1
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10.1002/adsc.201701162
Advanced Synthesis & Catalysis
Recently, we became interested in developing
whereas
the
Co-catalyzed
C-H
activation
cobalt-catalyzed heteroannulation reactions to
incorporate uncommon -organic components[13] and
while searching for suitable annulation partners,
heterobicyclic alkenes caught our attention because a
Co-catalyzed C-H activation of phosphinamides and
their annulation with 7-oxa/azabenzonorbornadienes
will give rapid access to phosphorous containing
heterocycles.[14] Despite the great synthetic utility of
heterobicyclic olefins in transition-metal catalyzed
stereoselective ring-opening reactions,[15,16] the use of
these substrates in C-H activation reactions as
annulation partners is relatively rare. In this context,
Li and co-workers studied Rh(III)-catalyzed C-H
activation of 2-arylpyridines and their subsequent
coupling with bicyclic olefins leading to 2-
naphthylated products or cis-dihydrocarbazoles.[17]
Following a similar strategy, an ortho-arylation of
arylphosphine derivatives with heterobicyclic alkenes
was illustrated by Miura and co-workers.[18]
Subsequently, Co(III)-catalyzed C-H naphthylation of
arenes was developed by the groups of Li and Cheng
independently (Scheme 1a).[19,20] In contrast,
hydroarylation reactions with heterobicyclic alkenes
were described by Bolm and co-workers employing
Rh(III) or Ru(II)-catalysts (Scheme 1b).[21] Very
recently, a Co-catalyzed diastereoselective [3+2]
cycloaddition of amides and bicylic alkenes was
reported by Cheng and co-workers (Scheme 1c).[22]
An interesting Rh(III)-catalyzed C-H activation and
Wagner-Meerwein type rearrangment was recently
demonstrated by Glorius and co-workers.[23]
arylsulfonamides and annulation with allenes
required 100 C.[13b] This is probably because of the
stronger
diarylphosphinamide to cobalt due to the relatively
lower acidity of diarylphosphinamide N-H in
comparison to that of arylsulfonamides.
o
binding
of
amide
nitrogen
of
Table 1: Substrate scope of diarylphosphinamidesa)
R
R
O
P
Q
Co(acac)2 (20 mol% )
Mn(OAc)3.2H2O (2 equiv )
N
O
2
H
R
O
P
NaOPiv (2 equiv )
TFE(2 mL), rt
HN
Q
H
R
+
O
1, 0.15 mmol
3
Ar
O
Ph
O
P
Q
P
Q
N
N
H
H
Me
H
H
O
O
3a, 85%, Ar = Ph
3b, 72%, Ar = 4-MePh
CCDC 1545563
Ar
O
Ar
O
Ar O
P
Q
P
Q
MeO
P
Q
N
N
N
H
H
H
Me
MeO
H
H
H
O
O
O
3c, 69%, Ar = 4-Et-Ph
3d, 67%, Ar = 4-OMe-Ph
3e, 88%, Ar = 3-OMe-Ph
Ar
O
Ar
O
Ar O
P
Q
P
Q
P
Q
N
N
N
H
H
H
F
Cl
Br
H
H
H
O
O
O
3f, 77%, Ar = 4-F-Ph
3g, 66%,
Ar = 4-Cl-Ph,
3h, 86%,
Ar = 4-Br-Ph,
These recent studies on the application of
heterocyclic olefins in C-H activation reactions and
the synthetic importance phosphaheterocycles,
prompted us to develop a Co-catalyzed C-H
activation methodology for the synthesis of these
derivatives and herein we report our studies on the
diastereoselective [4+2] annulation of aryl
phosphinamides with heterobicyclic alkenes through
Co-catalyzed C-H activation proceeding at room
temperature (Scheme 1d).
Ar
O
Ar
S
O
P
Q
P
Q
N
N
H
H
H
H
O
O
3i, 62%,
Ar = 2-Napthyl
CCDC 1545556
3j,74%,
Ar = 2-Thienyl
CCDC 1545560
a)
Reaction conditions: 1 (0.15 mmol), olefin (0.225 mmol),
Co(acac)2.4H2O (20 mol%), Mn(OAc)3.2H2O (0.3 mmol),
NaOPiv.H2O (0.3 mmol), TFE (2 mL), 48 h, isolated yield.
Our preliminary investigation focused on the C-
H
activation
and
annulation
of
After establishing the optimal reaction
conditions, we probed the substrate scope with a
variety of diarylphosphinamides 1 using 1,4-epoxy
dihydronaphthelene 2a. As shown in Table 1,
regardless of the electronic and steric factors,
different diarylphosphinamides 1a-1j were smoothly
coupled with 2a to afford the corresponding cyclic
phosphinamides 3a-3j in good to excellent yields (62-
88%). Several important functional groups such as
methoxy (3d, 3e), fluoro (3f), chloro (3g), and bromo
(3h) are compatible at different position of 1
providing ample opportunity for further derivatization
of the products. In the case of meta substituted
phosphinamide 1e, the reaction selectively occurred
at the less hindered position (3e). The reaction can
also be applied to 2-napthyl phosphinamide to obtain
3i in 62% yield. Gratifyingly, the reaction was not
diphenylphosphinamide 1a with readily available
bicyclic olefin, 1,4-epoxydihydronapthelene 2a and
tested the reaction using 20 mol% Co(acac)2, base
and oxidant in TFE.[13a] We were pleased to find that
using 2.0 equiv. of Mn(OAc)3 as oxidant and NaOPiv
as base, the product 3a can be isolated as a single
diastereomer in a promising yield of 85% (see
Supporting Information). The structure of 3a was
determined by single crystal X-ray diffraction studies,
which clearly indicated thermodynamically more
favourable exo isomer as the product.[24] The
combination of Mn(OAc)3 and NaOPiv was found to
be crucial as other oxidants or bases led to the
product 3a in lower yields. It is also worth
mentioning
that
the
C-H
activation
of
diarylphosphinamides proceeds at room temperature,
2
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10.1002/adsc.201701162
Advanced Synthesis & Catalysis
limited to arylphosphinamides and heteroaryl
phosphinamide like 2-thienyl phosphinamide
tolerated under the same conditions to provide the
expected annulated product (3j) in 74% yield. The
structure and the stereochemistry of the annulation
reaction were unambiguously confirmed by the
crystal structures of 3i and 3j.[24]
5b in 71% and 76% respectively. The reaction with
7-azobenzonorbornadienes also proceeded with
excellent diastereoselecitivity, providing the exo
isomer exclusively. The structure and stereochemistry
of the compound 5a was further confirmed by X-ray
crystallography.[24]
To further illustrate the substrate scope, the
reaction was examined with differently substituted 7-
oxabenzonorbornadiene derivatives 2 in reaction with
diarylphosphinamide 1 using 20 mol% of Co(acac)2,
2.0 equiv. of Mn(OAc)3, and 2.0 equiv. NaOPiv in
TFE at room temperature (Table 2). 7-
Oxabenzonorbornadienes with both electron-donating
and electron-withdrawing groups on the benzene ring
found to be suitable reaction partners affording the
corresponding products 3k-3r in 67-86% yields.
Methoxy or bromo susbtutitents are well tolerated
giving the corresponding products in good yields.
Furthermore, heterobicyclic alkene having four
substituents on the benzene ring led to the
corresponding phosphaheterocycle 3r in 67%.
Table 3: Substrate scope with 7-azobenzonorbornadienes.
R1
R1
O
P
Q
H
N
Co(acac)2 (20 mol% )
Mn(OAc)3.2H2O (2 equiv )
X
R1
O
P
HN
R1
Q
H
NaOPiv (2 equiv )
TFE(2 mL), rt
+
R2
X
R2
5, X = N-Boc, N-Ts
1, 0.15 mmol
4, X = N-Boc, N-Ts
Ar
H
O
Ar
H
O
P
Q
MeO
P
Q
H
N
N
H
Br
NTs
NBoc
5a, 71%, Ar = 4-Br-Ph
5b, 76%, Ar = 3-OMe-Ph
CCDC 1545632
To
further
demonstrate
the
synthetic
applicability of the Co-catalyzed [4+2] annulation
reaction, bicyclic phosphinamides 3 derived from 7-
oxabenzonorbornadienes were treated under acidic
conditions. After optimization, we found that using
Table 2: Substrate scope of 7-oxabenzonorbornadienesa)
R
R1
O
P
Q
H
Co(acac)2 (20 mol% )
Mn(OAc)3.2H2O (2 equiv )
N
O
o
R
O
triflic acid in chloroform at 70 C, benzo fused
P
HN
R1
NaOPiv (2 equiv )
TFE(2 mL), rt
Q
H
phosphaphenanthridinones 6 can be isolated in
excellent yields (85-87%) from the corresponding
phosphinamides 3 after dehydration. The reaction
sequence consists of an acid-mediated ring-opening
reaction followed by aromatization. The structure of
the compound 6c was assigned from the single-
crystal X-ray diffraction analysis.[24]
+
R2
O
2
3
1, 0.15 mmol
R2
Ph
H
O
Ph
O
Ph
H
O
P
Q
H
P
Q
H
P
Q
N
N
N
H
H
O
O
O
Me
OMe
Me
OMe
3l, 74%
Table 4: Ring opening/aromatization sequence
3a, 85%
3k, 74%
R1
Ar
O
Ar
O
Ar O
R1
P
Q
H
P
Q
H
P
Q
H
N
N
N
O
P
Q
O
N
N
P
Q
Me
MeO
Br
R1
CF3SO3H (10 equiv.)
H2O
+
R1
H
H
H
H
O
O
O
CHCl3 (2 mL), 70 °C, 2h
H
O
OMe
OMe
OMe
6
3
R2
OMe
OMe
OMe
R2
3m, 75%, Ar = 4-Me-Ph
3n, 70%, Ar = 4-OMe-Ph
3o, 86%, Ar = 4-Br-Ph
Yield
Product
Substrate
Ph
O
Ph
H
O
Ph
H
O
Ph
O
P
Q
H
P
Q
H
P
Q
H
N
N
N
Ph O
P
Q
N
P
Q
H
N
6a, 87%
H
O
O
O
CH3
Br
H
O
Br
H3C
3r, 67%
O
Me
O
Br
Br
Me
Me
3p, 71%
3q, 71%
Me
Q
Ph
O
a) Reaction conditions: 1 (0.15 mmol), olefin (0.225
mmol), Co(acac)2.4H2O (20 mol%), Mn(OAc)3.2H2O (0.3
mmol), NaOPiv.H2O (0.3 mmol), TFE (2 mL), 48 h, rt,
isolated yield.
Ph
O
P
Q
N
P
H
N
6b, 87%
H
O
CH3
Br
CH3
Br
H3C
H3C
Next, we investigated the scope of Co-catalyzed
[4+2] annulation of phosphinamides with 7-
azabenzonorbornadienes 4. As can be seen in Table 3,
both N-Boc and N-tosyl-protected azabicylic alkenes
reacted smoothly under the optimized reaction
conditions to give the corresponding products 5a and
Br
Br
Ar
O
Ar
O
P
Q
N
P
Q
H
N
MeO
6c, 85%
H
MeO
Ar = 4-OMe-Ph
O
CCDC 1545554
3
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10.1002/adsc.201701162
Advanced Synthesis & Catalysis
stir-bar, Co(acac)2 (7 mg, 20 mol%), Mn(OAc)3.2H2O (80
mg, 0.3 mmol), NaOPiv.H2O (37 mg, 0.3 mmol), and
diphenylphosphonamide 1a (50 mg, 0.15 mmol) were
added. 7-oxabenzonorbornadiene 2a (43 mg, 0.225 mmol)
was added to the reaction mixture followed by
trifluoroethanol (3 mL). The reaction tube was capped and
stirred at room temperature for 48 h. Upon completion, the
reaction mixture was evaporated under reduced pressure
and passed through the column chromatography for
purification on silica gel with petroleum ether and ethyl
acetate (20:80) mixture as the eluent, giving the product 3a
(62 mg, 85% yield)
The plausible reaction mechanism based on the
previous reports[25] is shown in Scheme 2 for the
cobalt-catalyzed [4+2] annulation reaction between
arylphosphinamides and heterobicyclic olefins. The
catalytic cycle is likely to begin with the anion
exchange of Co(II) with the acidic phosphinamide N-
H, facilitated by the coordination of 8-
aminoquinoline auxiliary to form the intermediate A,
which will be oxidized by Mn(OAc)3 to give the
Co(III) complex B. Subsequent base assisted C-H
bond cleavage leads to the five-membered
cobaltacycle intermediate
C
with concomitant
formation of PivOH. Coordinative insertion of the
double bond of 7-oxa/azabenzonorbornadiene 2 into a
D affords the seven
membered cobaltacycle intermediate E, which upon
reductive elimination gives the annulation product 3
or 5. Re-oxidation of Co(I) with the stoichiometric
oxidant regenerates the Co(II)-species.
Acknowledgements
This activity is supported by SERB (EMR/2015/002047, funding
to CMRV). Financial support was also received from DST-Fast
Track Scheme (NT).
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and highly diastereoselective cobalt-catalyzed [4+2]
annulation of diarylphosphinamides with 7-
oxa/azabenzonorbornadienes to prepare bridged
polycyclic phosphorous compounds. The reaction
proceeds under operationally simple conditions at
room temperature and tolerates a wide range of
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ring opening/aromatization sequence. Further
synthetic applicability and detailed mechanistic
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Experimental Section
Typical experimental procedure for the synthesis of 3a: In
an oven dried 10 mL reaction tube, charged with magnetic
4
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10.1002/adsc.201701162
Advanced Synthesis & Catalysis
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5
This article is protected by copyright. All rights reserved.

10.1002/adsc.201701162
Advanced Synthesis & Catalysis
COMMUNICATION
Cobalt-Catalyzed Diastereoselective [4+2]
Annulation of Phosphinamides with Heterobicyclic
Alkenes at Room Temperature
O
R
[4+2] Annulation
Co
O
R
P
Q
H
O
R
N
X
P
Q
N
P
Q
H
N
H
+
H
-H2O
X
H
Adv. Synth. Catal. 2017, Volume, Page – Page
X = O, N-PG
Aryl C-H activation
•
•
•
•
•
Room temperature
Excellent diastereoselectivity
Good functional group tolerance
Q =
R. Nallagonda, N. Thrimurtulu, C. M. R. Volla*
N
6
This article is protected by copyright. All rights reserved.