Rhodium-catalyzed arylative cyclization of alkynyl malonates by 1,4-rhodium(i) migration

Article abstract of DOI:10.1039/c9cc05205d

The synthesis of functionalized 1-tetralones by the rhodium(i)-catalyzed reaction of alkynyl malonates with arylboronic acids is described. These arylative cyclizations proceed via an alkenyl-to-aryl 1,4-Rh(i) migration as a key step. Preliminary results

Full text of DOI:10.1039/c9cc05205d

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Rhodium-catalyzed arylative cyclization of alkynyl malonates by
1,4-rhodium(I) migration†
Luke O’Brien,ab Somnath Narayan Karad,ab William Lewis,b and Hon Wai Lam*ab
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
OH
O
O
O
The synthesis of functionalized 1-tetralones by the rhodium(I)-
catalyzed reaction of alkynyl malonates with arylboronic acids is
described. These arylative cyclizations proceed via an alkenyl-to-
aryl 1,4-Rh(I) migration as a key step. Preliminary results of an
enantioselective variant of these reactions are also presented.
OMe
Me
Me
OH
O
Me
Me
OH
O
OH
(±)-nidemone
aspewentin B
diomuscinone
Fig 1
Natural products containing a 1-tetralone with an all-carbon
quaternary stereocenter at C2
Domino reactions that consist of a metal-catalyzed addition of an
aryl nucleophile to an alkyne, followed by an intramolecular
nucleophilic addition of the resulting alkenylmetal species onto a
tethered electrophile, are versatile transformations for the
preparation of hetero- and carbocyclic products.1 A variation of these
arylative cyclizations involves the 1,4-migration of the metal2 from
the initially formed alkenylmetal species A onto an aryl site,
followed by cyclization of the resulting arylmetal species B onto the
electrophile (Scheme 1A). This through-space transmission of
reactivity further increases the synthetic capabilities of arylative
cyclizations, and to date, reactions based upon alkenyl-to-aryl 1,4-
migrations of rhodium,3 iridium,4 and cobalt5 have been
described.6,7,8,9,10,11 The use of esters as the electrophiles in these
reactions leads to the formation of aromatic ketones. In this context,
the Murakami3a and Yoshikai5 groups have shown that alkyne-
tethered esters react with arylboron and arylzinc reagents in arylative
cyclizations under rhodium and cobalt catalysis, respectively.
However, only symmetrical alkynes were employed in these
studies.3a,5 Although this feature eliminates the challenge of
controlling regioselectivity in the initial arylmetalation, it does limit
synthetic utility. Here, we describe the rhodium-catalyzed reaction of
arylboronic acids with alkynyl malonates 1, in which the alkyne is
unsymmetrically substituted (Scheme 1B). These arylative
cyclizations produce 1-tetralones containing an all-carbon quaternary
stereocenter at C2, a structural motif that appears in several natural
products such as (±)-nidemone,12 aspewentin B,13 and
diomuscinone14 (Figure 1). Preliminary results of an enantioselective
variant are also described.
A. Catalytic arylative cyclizations via 1,4-metal migration
E: electrophile
R1
R1
R1
R1
MLn
H
E
MLn (cat.)
+
E
H
MLn
E
E
swap
Ar
Ar
B
Ar
A
Z
Ar
arylboron or arylzinc
It is known that carbometalation of alkynes substituted with one
alkyl and one aryl group are often highly regioselective.15
Accordingly, bis(2,2,2-trifluoroethyl)malonate 1a, which contains
such an alkyne, was selected for our initial experiments in the hope
that a highly regioselective synthesis of 1-tetralones by arylative
cyclization could be achieved. First, a mixture of 1a and PhB(OH)2
(1.5 equiv) was heated at 70 °C for 20 h in the presence of 5 mol%
of [Rh(cod)Cl]2 and various bases (1.5 equiv) (Table 1).16 We were
pleased to observe that arylative cyclization was successful and the
best results were obtained using KF as the base in 1,4-dioxane/H2O
(9:1) as the solvent, which gave 1-tetralone 2aa in 75% yield as
B. Rh(I)-catalyzed synthesis of tetralones by arylative cyclization (this work)
O
O
O
R2
CO2R1
KF (1.5 equiv)
[Rh(cod)Cl]2 (5 mol%)
R1O
OR1
+
R2
Ar
(HO)2B
(1.5 equiv)
Ar
1,4-dioxane/H2O (9:1)
70 °C, 20 h
Ar
1
2
also see refs 3a and 5
Ar
Scheme 1 Catalytic arylative cyclizations via 1,4-metal migration
a. The GlaxoSmithKline Carbon Neutral Laboratories for Sustainable Chemistry,
University of Nottingham, Jubilee Campus, Triumph Road, Nottingham, NG7 2TU,
United Kingdom
1
b. School of Chemistry, University of Nottingham, University Park, Nottingham, NG7
2RD, United Kingdom
determined by H NMR analysis of the crude mixture using 1,4-
dimethoxybenzene as an internal standard (entry 1). This experiment
also gave alkyne hydroarylation product 3ab in 14% yield. Changing
the quantity of H2O in the reaction medium by using anhydrous
† Electronic Supplementary Information (ESI) available: Experimental procedures,
full spectroscopic data for new compounds, and crystallographic data for 2ea.
CCDC 1938497. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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Table 1 Evaluation of reaction conditionsa
Table 2 Scope with respect to the alkynyl malonatea
View Article Online
O
O
O
O
DOI: 10.10
O
39/C9CC05205D
R2
KF (1.5 equiv)
[Rh(cod)Cl]2 (5 mol%)
R1O
OR1
CF3CH2O
Ph
OCH2CF3
PhB(OH)2 (1.5 equiv)
CO2R1
+
R2
Bn
1,4-dioxane/H2O (9:1)
70 °C, 20 h
KF (1.5 equiv)
Ar
1
1a
[Rh(cod)Cl]2 (5 mol%)
1,4-dioxane/H2O (9:1)
70 °C, 20 h
2
+
Ar
PhB(OH)2 (1.5 equiv)
O
O
O
O
O
O
67%b
58%
50%
36%c
55%
Bn
R
CO2CH2CF3
2aa R = Ph
2ba R = H
2ca R = 2-thienyl
2da R = COPh
2ea R = CO2Ph
CO2CH2CF3
CF3CH2O
OCH2CF3 CF3CH2O
OCH2CF3
Bn
Ph
Bn
+
+
Ph
Ph
Ph
Ph
Ph
3ab
2aa
3aa
O
O
Ar
CO2CH2CF3
Entry Deviation from
Yield of 2aa Yield of 3aa Yield of 3ab
2fa Ar = Ph
62%
standard conditions
None
(%)b
75
(%)b
–
(%)b
14
14
9
2ga Ar = 2-MeOC6H4
2ha Ar = 2-naphthyl
2ia Ar = 3-thienyl
54%
56%d
57%
1
2
3
4
5
6
7
1,4-Dioxane as solvent
42
19
5
Ph
Bn
In 1,4-dioxane/H2O (4:1) 54
2ja Ar = 4-MeOC6H4
2ka Ar = 3-MeC6H4
2la Ar = 1-naphthyl
2ma Ar = 2-thienyl
64%
74%
68%
66%
Toluene as solvent
Xylenes as solvent
Et3N instead of KF
Cs2CO3 instead of KF
28
33
47
56
28
42
19
–
14
14
14
9
CO2CH2CF3
Ar
O
a Reactions were conducted with 0.05 mmol of 1a. b Determined by 1H NMR
analysis of the crude reactions using 1,4-dimethoxybenzene as an internal
standard.
CO2Ph
CO2Me
2na
72%
Ph
1,4-dioxane or 1,4-dioxane/H2O (4:1) gave lower yields of 2aa along
with significant quantities of alkyne hydroarylation products 3aa and
3ab (entries 2 and 3). Other solvents such as toluene (entry 4) and
xylenes (entry 5) also gave inferior results. Other bases such as Et3N
(entry 6) and Cs2CO3 (entry 7) are also effective but the yields of
2aa are appreciably lower compared with using KF (entry 1). The
conditions shown in entry 1 were therefore selected for use in further
experiments.
O
O
Me
CO2Ph
2oa
2pa
55%
Ph
OEt
CO2CH2CF3
36%d
The scope of this reaction with respect to the alkynyl malonate
was then examined in reactions with PhB(OH)2, which gave 1-
tetralones 2aa–2qa in 33–74% yield (Table 2). In some cases (2ha
and 2pa), it proved beneficial to increase the loading of [Rh(cod)Cl]2
to 10 mol% and the quantity of PhB(OH)2 to 2.0 equivalents. The
reaction producing 2aa also gave a 1:1.25 mixture of inseparable
alkyne hydroarylation products 3aa and 3ab (see Table 1 for the
structures), respectively, in 19% combined yield. Alkyne
hydroarylation products corresponding to 3aa and 3ab were not
isolated in subsequent experiments using other substrates. The
reaction is tolerant of a wide range of carbon-linked substituents at
the 2-position of the substrate, including benzyl (2aa and 2ja–2ma),
methyl (2ba and 2oa), 2-thienylmethyl (2ca), 2-oxo-2-phenylethyl
(2da), 2-oxo-2-phenoxyethyl (2ea17 and 2na), phenyl (2fa), 2-
methoxyphenyl (2ga), 2-naphthyl (2ha), and 3-thienyl (2ia) groups.
Heteroatom substituents at the 2-position are also accommodated,
such as ethoxy (2pa) and 3-thienylmethoxy (2qa) groups. The
alkynyl substituent can be changed from a phenyl group (2aa–2ia
and 2na–2qa) to 4-methoxyphenyl (2ja), 3-methylphenyl (2ka), 1-
naphthyl (2la), and 2-thienyl (2ma) groups. A substrate with a
methyl-substituted alkyne did undergo arylative cyclization in low
yield but the product 2ra contained unidentified, inseparable
impurities.18 In addition, a substrate containing a terminal alkyne
gave only a complex mixture of unidentified products. Pleasingly,
the reaction is not limited to bis(2,2,2-trifluoroethyl) malonates;
Ph
S
O
O
2qa
33%c
CO2CH2CF3
Ph
a
Reactions were conducted with 0.30 mmol of 1a–1q in 3 mL of 1,4-
b
dioxane/H2O (9:1). Yields are of isolated products. This experiment also
gave a 1:1.25 inseparable mixture of 3aa and 3ab, respectively, in 19%
combined yield. c The reaction time was 24 h. d Conducted using 10 mol% of
[Rh(cod)Cl]2 and 2.0 equiv of PhB(OH)2.
substrates containing dimethyl or diphenyl malonates gave 1-
tetralones 2na and 2oa in 55% and 72% yield, respectively.
Table 3 presents the results of the reactions of representative
substrates 1a, 1i, 1m, and 1n with various arylboronic acids, which
gave 1-tetralones 2ab–2nj in 45–79% yield. The arylboronic acid
scope includes a range of para- (2ab, 2ac, 2nh, and 2ni), meta-
(2mg), and disubstituted phenylboronic acids (2ie and 2mf)
containing methyl (2ab), halide (2ac, 2mf, and 2ni), carboethoxy
(2mg), or alkoxy groups (2ge and 2nh). 2-Naphthylboronic acid
(2ad) is also tolerated. In the case of 2-naphthylboronic acid and 3-
ethoxycarbonylphenylboronic acid, 1,4-Rh(I) migration occurred to
the sterically more accessible position (2ad and 2mg, respectively).
3-Thienylboronic acid also reacted successfully with 1a; however,
2 | J. Name., 2012, 00, 1-3
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Table 3 Scope with respect to the boronic acida
generate rhodium hydroxide 4 (R = H), which ViceawnArtiuclnedOenrlginoe
transmetalation with PhB(OH)2 to give arylrhodium species 5.
DOI: 10.1039/C9CC05205D
O
O
O
R2
CO2R1
Phenylrhodation of the alkyne of 1a gives alkenylrhodium species 6,
which then undergoes alkenyl-to-aryl 1,4-Rh(I) migration to give
arylrhodium species 7. Cyclization of 7 by 1,2-addition onto one of
the esters produces rhodium alkoxide 8, which collapses to release
the product 2aa and regenerate the active rhodium complex 4 (which
could have a either a trifluoroethoxide or hydroxide counterion).
R1O
OR1
KF (1.5 equiv)
R2
[Rh(cod)Cl]2 (5 mol%)
Ar
Ar1
1,4-dioxane/H2O (9:1)
70 °C, 20 h
1a, 1i, 1m or 1n
+
Ar2B(OH)2 (1.5 equiv)
2
Ar1
O
Bn
CO2CH2CF3
R
O
0.5 [Rh(cod)Cl]2
KF, H2O
KCl + HF
PhB(OH)2
ROB(OH)2
2ab R = Me
2ac R = F
79%
68%
Bn
CO2CH2CF3
+
ROH
Ph
LnRh OR
O
4
Ph
H2O
2aa
Bn
CO2CH2CF3
O
O
R = H or CH2CF3
2ad
56%
LnRh Ph
CF3CH2O
Ph
OCH2CF3
5
CF3CH2O ORhLn
Bn
Bn
1a
Ph
CO2CH2CF3
S
O
Bn
O
CF3CH2O
O
8
MeO
Ph
CO2CH2CF3
2ie
50%
51%
OCH2CF3
Ph
LnRh
MeO
O
CF3CH2O
O
Ph
H
6
O
OCH2CF3
Bn
CO2CH2CF3
Bn
1,4-migration
Cl
Cl
Ph
2mf
H
LnRh
7
S
Scheme 2 Possible catalytic cycle
O
Bn
CO2CH2CF3
Finally, preliminary efforts at developing an enantioselective
variant of this reaction were conducted. After some
experimentation,19 heating 1a with PhB(OH)2 (1.5 equiv) in the
presence of [Rh(C2H4)2Cl]2 (5 mol%), (R)-MeO-BIHEP (L1, 10
mol%), and KF (1.5 equiv) in 1,4-dioxane/H2O (9:1) at 70 °C gave
(+)-2aa in 85% yield and 76% ee, along with an inseparable mixture
of 3aa and 3ab in 13% yield (eqn (2)).
2mg
56%
EtO
O
S
O
CO2Ph
CO2Me
R
2nh R = OMe
2ni R = Cl
51%
45%
Ph
MeO
MeO
PPh2
PPh2
O
O
a
Reactions were conducted with 0.30 mmol of 1a, 1g, 1m or 1n in 3 mL of
1,4-dioxane/H2O (9:1). Yields are of isolated products.
CF3CH2O
Ph
OCH2CF3
Bn
L1 (10 mol%)
O
1a
[Rh(C2H4)2Cl]2 (5 mol%)
KF (1.5 equiv)
1,4-dioxane/H2O (9:1)
70 °C, 20 h
Bn
CO2CH2CF3
+
(2)
S
PhB(OH)2 (1.5 equiv)
O
O
CF3CH2O
Ph
OCH2CF3
Ph
O
Bn
O
O
O
O
Bn
CO2CH2CF3
KF (1.5 equiv)
[Rh(cod)Cl]2 (5 mol%)
2aj 21%
1a
CF3CH2O
Ph
OCH2CF3 CF3CH2O
OCH2CF3
*
(1)
+
+
1,4-dioxane/H2O (9:1)
70 °C, 20 h
Bn
Ph
Bn
+
+
S
O
B(OH)2
(1.5 equiv)
Bn
CO2CH2CF3
S
Ph
Ph
(+)-2aa 85%, 76% ee
Ph
3aa
3ab
(3aa + 3ab) 13%
3aa:3ab = 1:20
Ph
2aj' 42%
In summary, we have developed the rhodium(I)-catalyzed
reaction of alkynyl malonates with arylboronic acids to give diverse
1-tetralones. A key step in these arylative cyclizations is an alkenyl-
to-aryl 1,4-Rh(I) migration. Use of a chiral bisphosphine-ligated
rhodium complex as the precatalyst gives promising
enantioselectivity (76% ee). Our investigations into development of
two products 2aj and 2aj' were obtained in 21% and 42% yield,
respectively, resulting from 1,4-Rh(I) migration to different sites of
the thiophene prior to cyclization (eqn (1)).
A possible catalytic cycle for these reactions is depicted in
Scheme 2, using substrate 1a and PhB(OH)2 as example reaction
partners. Heating a mixture of [Rh(cod)Cl]2, KF, and H2O may
This journal is © The Royal Society of Chemistry 20xx
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new domino reactions involving 1,4-metal migration are ongoing
and will be reported in due course.20
View Article Online
DOI: 10.1039/C9CC05205D
Zhang, J.-F. Liu, A. Ugrinov, A. F. X. Pillai, Z.-M. Sun and P. Zhao, J.
Am. Chem. Soc., 2013, 135, 17270-17273. (h) R. Shintani, R. Iino and K.
Nozaki, J. Am. Chem. Soc., 2014, 136, 7849-7852. (i) H. B. Hepburn and
H. W. Lam, Angew. Chem., Int. Ed., 2014, 53, 11605-11610. (j) A.
Masarwa, M. Weber and R. Sarpong, J. Am. Chem. Soc., 2015, 137,
6327-6334. (k) B. M. Partridge, M. Callingham, W. Lewis and H. W.
Lam, Angew. Chem., Int. Ed., 2017, 56, 7227-7232. (l) M. Callingham,
B. M. Partridge, W. Lewis and H. W. Lam, Angew. Chem., Int. Ed.,
2017, 56, 16352-16356. (m) J. L. Ming, Q. Shi and T. Hayashi, Chem.
Sci., 2018, 9, 7700-7704. (n) T. Miwa and R. Shintani, Org. Lett., 2019,
21, 1627-1631. (o) S.-S. Zhang, T.-J. Hu, M.-Y. Li, Y.-K. Song, X.-D.
Yang, C.-G. Feng and G.-Q. Lin, Angew. Chem., Int. Ed., 2019, 58,
3387-3391.
For examples of 1,4-rhodium(III) migration, see: (a) D. J. Burns and H.
W. Lam, Angew. Chem., Int. Ed., 2014, 53, 9931-9935. (b) D. J. Burns,
D. Best, M. D. Wieczysty and H. W. Lam, Angew. Chem., Int. Ed., 2015,
54, 9958-9962. (c) S. E. Korkis, D. J. Burns and H. W. Lam, J. Am.
Chem. Soc., 2016, 138, 12252-12257. (d) J. D. Dooley and H. W. Lam,
Chem. Eur. J., 2018, 24, 4050-4054. (e) J. Q. Sun, D. C. Bai, P. Y.
Wang, K. Wang, G. F. Zheng and X. W. Li, Org. Lett., 2019, 21, 1789-
1793. (f) D. C. Bai, J. T. Xia, F. F. Song, X. Y. Li, B. X. Liu, L. H. Liu,
G. F. Zheng, X. F. Yang, J. Q. Sun and X. W. Li, Chem. Sci., 2019, 10,
3987-3993.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This work was supported by the Engineering and Physical Sciences
Research Council (EPSRC) Centre for Doctoral Training in
Sustainable Chemistry [grant number EP/S022236/1] through a PhD
studentship to L.O.; the European Union’s Horizon 2020 research
and innovation programme [grant number 702386] through a Marie
Skłodowska-Curie Individual Fellowship to S.N.K.; the University
of Nottingham; and GlaxoSmithKline.
7
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9
For examples of other types of 1,4-iridium (I) migration, see ref. 6l and:
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CCDC 1938497†.
5
6
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18 See the Supplementary Information for further details.
19 For further details about the evaluation of chiral ligands in these
reactions, see the Supplementary Information.
20 The research data associated with this publication can be found at DOI:
10.17639/nott.7008
4 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C9CC05205D
O
O
O
O
via:
O
Bn
CO2CH2CF3
CF3CH2O
OCH2CF3
CF3CH2O
OCH2CF3
KF (1.5 equiv)
[Rh(cod)Cl]2 (5 mol%)
Bn
Bn
+
1,4-dioxane/H2O (9:1)
70 °C, 20 h
S
PhB(OH)2 (1.5 equiv)
66%
S
[Rh] H
27 examples
S
swap
The synthesis of functionalized 1-tetralones by the rhodium(I)-catalyzed reaction of alkynyl malonates with arylboronic acids
is described.