Asymmetric Alkenylation of Enones and Imines Enabled by A Highly Efficient Aryl to Vinyl 1,4-Rhodium Migration

Article abstract of DOI:10.1002/anie.201813585

The asymmetric rhodium-catalyzed alkenylation of enones and imines with arylboronic acids has been developed. A highly controllable aryl to vinyl 1,4-rhodium migration is the key step. Stereodefined vinyl moieties were installed in excellent enantioselectivies for most examined examples. DFT calculations reveal that the driving force of this rhodium migration is a kinetically favored process.

Full text of DOI:10.1002/anie.201813585

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Accepted Article
Title: Asymmetric Alkenylation of Enones and Imines Enabled by
Highly Efficient Aryl to Vinyl 1,4-Rhodium Migration
Authors: Shu-Sheng Zhang, Tian-Jiao Hu, Meng-Yao Li, Yi-Kang
Song, Xiao-Di Yang, Chenguo Feng, and Guo-Qiang Lin
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201813585
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10.1002/anie.201813585
Angewandte Chemie International Edition
DOI: 10.1002/anie.200((will be filled in by the editorial staff))
Metal Migration
Asymmetric Alkenylation of Enones and Imines Enabled by Highly
Efficient Aryl to Vinyl 1,4-Rhodium Migration**
Shu-Sheng Zhang,§ Tian-Jiao Hu,§ Meng-Yao Li, Yi-Kang Song, Xiao-Di Yang, Chen-Guo Feng* and
Guo-Qiang Lin*
Enantioselective rhodium-catalyzed addition of organoboron
reagents to electron-deficient double bonds has proven to be a
powerful and reliable method for asymmetric carbon-carbon bond
construction.[1] Compared to the wide application of arylboronates,
vinylboronates are far less studied, and quite limited with easily
accessible ones bearing a di-substituted double bond.[2] When
vinylboronates with more substitutions on the double bond are
needed, one of the challenges aroused is to control the olefin
stereochemistry. Although several methods to effectively prepare
these vinylboronates have been released,[3] new and even more
ingenious strategies to address this issue are always desirable.
In rhodium catalysis, new reactivity of the original
organoboronates sometimes can be pursued by rhodium migration
approach, and achieve synthetic transformations that are
inaccessible by conventional methods. In 2012, Hayashi and co-
workers reported a vinyl to aryl 1,4-rhodium migration starting from
a vinylboronic acid, which provided a novel method to add an ortho-
vinyl substituted phenyl ring to enones (Scheme 1a).[4] In 2014, Lam
and co-workers described an allyl to allyl 1,4-rhodium migration
and realized a complicated allylation of cyclic imines with simple
allylic boronates (Scheme 1b).[5] We envisioned that an aryl to vinyl
rhodium migration could occur for the corresponding arylboronates,
providing a new method to attach multi-substituted vinyl moiety
with controllable stereochemistry of the double bond (Scheme 1c).
Since the pioneering work of Miura,[6] rhodium migration has
been extensively explored.[7-12] Vinyl to aryl 1,4-rhodium migration
is one of the most studied migration mode in this field, and has been
applied in many novel organic transformations.[8] In contrast, the
reverse approach, application of aryl to vinyl 1,4-rhodium migration
in organic synthesis, has not been reported yet,[13] probably because
the aryl position is normally more thermodynamically favoured.
Recently, we discovered an aryl to vinyl 1,4-palladium migration
and applied in the stereoselective synthesis of vinylboronates and
1,3-dienes.[14] We speculate that the key to success is the use of
terminal olefins, and the driving force for this migration process
likely comes from faster cross-coupling for less sterically hindered
vinyl palladium compared to the corresponding aryl palladium
species.
Scheme 1. New reactivity of organoboronates enabled by 1,4-
rhodium migration
[]
Dr. S.-S. Zhang, Mr. Y.-K. Song, Prof. X.-D. Yang, Prof. C.-
G. Feng, Prof. G.-Q. Lin
Innovation Research Institute of Traditional Chinese
Medicine, Shanghai University of Traditional Chinese
Medicine, Shanghai 201203 (China)
E-mail: fengcg@shutcm.edu.cn; lingq@sioc.ac.cn
Dr. T.-J. Hu, Mr. M.-Y. Li, Prof. C.-G. Feng, Prof. G.-Q. Lin
Key Laboratory of Synthetic Chemistry of Natural
Substances, Center for Excellence in Molecular Synthesis,
Shanghai Institute of Organic Chemistry, University of
Chinese Academy of Sciences, Chinese Academy of
Sciences, Shanghai 200032 (China)
[§] These authors contributed equally to this work.
Scheme 2. Proposed strategy.
Therefore, we think that a similar strategy is also possible for
enabling aryl to vinyl 1,4-rhodium migration (Scheme 2). When the
arylrhodium species 2 is generated through transmetalation with the
arylboronates 1, the following direct addition to electron-deficient
double bonds may be hampered by the ortho-vinyl substitution. In
this case, an oxidative addition of the adjacent vinyl C-H bond may
be triggered to form 4, which has been well established by
experimental and theoretical investigations.[15] The subsequent H-
transfer of 4 leads to the completion of the 1,4-rhodium migration.
Although the resulting vinyl rhodium 3 is supposed to be less stable
compared to the arylrhodium, the faster and favored addition to
electron-deficient double bonds would push the whole reaction
toward this migration path.
[] This work was supported by the National Natural Science
Foundation of China (21572253, 21772216), the Strategic
Priority Research Program of the Chinese Academy of
Sciences
(XDB
20020100),
the
973
Program
(2015CB856600), the STCSM (18401933500), The Key
Research Program of Frontier Science (QYZDY-SSW-
SLH026) and the Collaborative Innovation Center of
Chemical Science and Engineering (Tianjing). We thank
Prof. C. Li (FJIRSM of CAS) for his kind help in DFT
calculations and Dr. Han-Qing Dong (Arvinas, Inc.) for his
help in the preparation of this manuscript.
Supporting information for this article is available on the
WWW under http://www.angewandte.org or from the
1
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10.1002/anie.201813585
Angewandte Chemie International Edition
To test our hypothesis, the addition of arylboronic acid 6a to 2-
cyclohexenone 5a was explord as a model reaction, and a number of
rhodium catalysts were examined (Table 1). Delightfully, the
desired 1,4-rhodium migration/addition product 7a was produced in
excellent yield by using simple [RhCl(COD)]2 as catalyst (entry 1).
Only trace amounts of possible undesirable addition product 8a was
was introduced to para-position (7e - 7h). The phenyl ring A could
be replaced by a naphthyl (7i), thienyl (7j) or pyridyl (7k) group
without affecting the reaction outcome. However, replacement with
alkyl substitutions still offered high enantioselectivities albeit with
lower reaction yields (7l and 7m), which partially was attributed to
the incomplete conversion of enone 5a. In comparison, substitutions
on the phenyl ring B showed significant impact on the reaction
activity. Introduction of a substituent generally led to a reduced
reaction yield, especially with an electron-withdrawing group (like
7p and 7q), however excellent enantioselectivities were maintained.
The substitution on the phenyl ring B changes electronic property of
C-B/C-Rh bond, which may increase the difficulty of rhodium
migration, as well as accelerate the hydrolysis of the
arylboronates.[19]
1
detected by H NMR and GC-MS analysis, and this is also the case
in the following studies using chiral catalysts. The in situ prepared
chiral rhodium catalyst from the reaction of [RhCl(C2H4)2]2 and
optically pure bicycle[3.3.0] octadiene L1[16] gave good
enantioselectivity, albeit with low yield (entry 2), which may
attributed to the huge steric hindrance of diene L1 for the
attachment of a bulky vinyl moiety. Higher reactivity was achieved
when dienes L2[17] and L3[18] were used, and an excellent
enantioselectivity was obtained with diene L3 (entries 3 and 4). In
contrast to fact that BINAP/rhodium complex failed to promote
vinyl to aryl 1,4-rhodium migration,[4] excellent performances of
BINAP and its derivatives were observed in our aryl to vinyl
rhodium migration process, and almost quantative yields and perfect
enantioselectivities were obtained for all the tested examples (entries
5-7). Reducing the catalyst loading to 3 mol % resulted in an
obvious loss in reaction yield(entry 8). It is worth mentioning that
only a single E-isomer was obtained in this migration/addition
process.
Table 1. Optimization of reaction conditions.[a]
Entry
Rhodium catalyst
Yield of
ee of 7a
7a/8a[d]
7a (%)[b]
(%)[c]
1
[RhCl(COD)]2
97
17
95
99
99
99
99
82
--
-93
87
97
98
99
99
99
>20/1
>20/1
>20/1
>20/1
>20/1
>20/1
>20/1
>20/1
2
[RhCl(C2H4)2]2/L1
[RhCl(C2H4)2] 2/L2
[RhCl(C2H4)2] 2/L3
[RhCl(C2H4)2] 2/L4
[RhCl(C2H4)2] 2/L5
[RhCl(C2H4)2] 2/L6
[RhCl(C2H4)2] 2/L6
3
4
5
6
7
8[e]
[a] Unless otherwise noted, reactions were carried out with 5a (0.20
mmol), 6a(0.40 mmol), cesium carbonate (0.30 mmol), [RhCl(COD)]2
(2.5 mol %) or [RhCl(C2H4)2]2 (2.5 mol %)/ligand (5.5 mol %) in
dioxane (2 mL)/H2O(0.1 mL) at 70 oC for 3 h. [b] Yields were
determined by 1H NMR spectroscopy analysis using CH2Br2 as an
internal standard. [c] Ee values were determined by chiral HPLC. [d]
Determined by 1H NMR spectroscopy and GC-MS analysis [e]
[RhCl(C2H4)2]2 (1.5 mol%)/L6 (3.3 mol %) and a prelonged reaction
time of 4 h.
Next, the generality of this rhodium migration/addition sequence
was examined under the optimized reaction conditions (Table 1,
entry 7). In all tested cases, the desired 1,4-rhodium
migration/addition reaction proceeded smoothly (Scheme 3).
Increasing steric hindrance by moving the para-methyl group in the
phenyl ring A to the meta or ortho-position had no negative effect
on both reaction yields and enantioselectivities (7a vs 7c and 7d).
Excellent reaction yields and enantioselectivities were also observed
no matter either electron-donating or electron-withdrawing group
Scheme 3. Alkenylation of enones via aryl to 1,4-rhodium migration.
Unless otherwise noted, reactions were carried out with 5 (0.20 mmol),
6 (0.40 mmol), [RhCl(C2H4)2]2 (2.5 mol %)/L6 ( 5.5 mol %) and
Cs2CO3 (0.30 mmol) in dioxane (2 mL)/H2O(0.1 mL) at 70 oC for 3 h.
[a] A small amount of unreacted enone 6 can be observed by 1H NMR
analysis of the crude product. [b] A prelonged reaction time of 5 h.
2
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10.1002/anie.201813585
Angewandte Chemie International Edition
Scheme 5. Mechanistic rationale supported by DFT calculations at the B3LYP/Def2TZVP//B3LYP/B1 level (B1: SDD-6-31G(d,p)). The
relative free energies are given in kcal/mol. The preferred pathway is shown in red.
The absolute configuration of 7c was unambiguously
determined to be R by X-ray crystallography (Figure 1),[20] which is
While other cyclic enones (7v and 7w, Scheme 3) were also
qualified as excellent coupling partners,
efficiency was observed for less reactive but more flexible linear
enones (7x and 7y).
a slightly reduced
in accordance to the stereochemistry-defining model for the
arylation of cyclohexenone previously proposed by Hayashi
group.[21] The configurations of other cyclohexenone adducts were
also assigned as R by assuming a similar reaction pathway.
Encouraged by the above success, the addition to less active
imine was also studied (Scheme 4). In this case, [Rh(OH)(COD)]2
proved to be the best precatalyst and DIFLUORPHOS (5,5'-
bis(diphenylphosphanyl)-2,2,2',2'-tetrafluoro-4,4'-bi[benzo-1,3-
dioxolyl]) was crucial for the reactivity. Under the newly optimized
reaction conditions, several arylboronic acids were tested for the
addition to cyclic imine 9. The desired rhodium migration/addition
sequence went very well for most examined examples, affording the
adducts 10 in good reaction yields with excellent enantioselectivities.
But the reactivity was greatly inhibited by a methyl substitution on
the phenyl ring B, and 5 equivalents of boronic acid 6 were needed
for a decent reaction yield.
Figure 1. X-ray crystal structure of 7c at the 50% probability level.
Hydrogen atoms have been omitted for clarity.
DFT calculations were performed to gain mechanistic insights
into this 1,4-rhodium migration process (Scheme 5).[22] Aided by
experimental data, a model system with COD as ligand was
constructed for simplification. Starting from the aryl rhodium
intermediate Int0, which was generated by transmetalation between
rhodium catalyst and arylboronic acid 6a,[23] two different pathways
A and B would afford direct 1,4-addition product 8a and 1,4-
rhodium migration/1,4-addition product 7a, respectively. In the
pathway A, the overall energy barrier for the direct insertion of 2-
cyclohexenone to C-Rh bond is 23.1 kcal/mol. While in the pathway
B, the 1,4-rhodium migration of Int0 includes a C-H oxidative
addition[4] and H-transfer sequence with an overall energy barrier of
21.1 kcal/mol,[4, 15] which is slightly lower than the direct addition
process. The resulting vinyl rhodium Int5 is thermodynamically less
stable than the original aryl rhodium Int0 (+3.3 kcal/mol vs 0
kcal/mol), which may be attributed to a stronger stabilizing effect of
phenyl group as well as the additional stabilizing effect from the
coordination of the vinyl group in Int0. Although the reverse
migration (Int5 → Int0) seems to be energetically favourable, the
much lower energy barrier (+13.2 kcal/mol) for the subsequent
addition of Int5 to 2-cyclohexone leads to a quick conversion of
Int5 to the desired alkenylation product, in other words, this facile
Scheme 4. Alkenylation of imine 9 via aryl to 1,4-rhodium migration.
Reactions were carried out with 9 (0.20 mmol), 6 (0.60 mmol),
[Rh(OH)(COD)]2 (2.5 mol %)/L7 ( 5.5 mol %), and Na2CO3 (0.30
o
mmol) in dioxane (2 mL) at 70 C for 5.5 - 8 h. [a] Conversions were
calculated by 1H NMR analysis of the crude products to be 90% (10b),
90% (10c) and 78% (10e), respectively. [b] 6 (1.00 mmol) was used.
3
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10.1002/anie.201813585
Angewandte Chemie International Edition
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catalyzed alkenylation of enones and imines with arylboronic acids.
A highly efficient aryl to vinyl 1,4-rhodium migration is the key to
success, providing
a new mode to generate stereodefined
vinylrhodium species. Both diene and bis-phosphine ligands proved
to be competent to promote this rhodium migration sequence, and
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Received: ((will be filled in by the editorial staff))
Published online on ((will be filled in by the editorial staff))
Keywords: asymmetric catalysis · rhodium· alkenylation · C-H
functionalization · metal migration
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4
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10.1002/anie.201813585
Angewandte Chemie International Edition
Metal Migration
Shu-Sheng Zhang,§ Tian-Jiao Hu,§
Meng-Yao Li, Yi-Kang Song, Xiao-Di
Yang, Chen-Guo Feng* and Guo-Qiang
Lin*
__________ Page – Page
Asymmetric Alkenylation of Enones and
Imines Enabled by Highly Efficient Aryl
to Vinyl 1,4-Rhodium Migration
The asymmetric rhodium-catalyzed alkenylation of enones and imines with
arylboronic acids has been developed. An highly controllable aryl to vinyl 1,4-
rhodium migration is the key step. Stereodefined vinyl moieties were installed in
excellent enantioselectivies for most examined examples. DFT calculations reveal
that the driving force of this rhodium migration is a kinetically favored process.
5
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