Rh-Catalyzed Regioselective Dialkylation of Cage B-H bonds in o-Carboranes: Oxidative Heck Reactions via an Enol Isomerization

Article abstract of DOI:10.1021/acs.orglett.9b03009

In the presence of a carboxylic acid directing group, Rh-catalyzed regioselective directed dialkylation of B(4,5)-H bonds in o-carboranes and oxidative coupling with allylic alcohols is reported. This strategy constructs a series of 4,5-dialkylated o-carboranes in good yields with excellent regioselectivity. A possible catalytic cycle is proposed that involves a tandem sequence of Rh-catalyzed cage B-H activation, alkene insertion, selective β-H elimination, enol isomerization, and decarboxylation.

Full text of DOI:10.1021/acs.orglett.9b03009

Letter
pubs.acs.org/OrgLett
Cite This: Org. Lett. XXXX, XXX, XXX−XXX
Rh-Catalyzed Regioselective Dialkylation of Cage B−H bonds in
o‑Carboranes: Oxidative Heck Reactions via an Enol Isomerization
Qian Wang,† Song Tian,† Chuyi Zhang,† Jiangwei Li,† Zhixuan Wang,† Yongmei Du,† Ling Zhou,‡
and Jian Lu*,†
†State Key Laboratory of Fluorine & Nitrogen Chemicals, Xi’an Modern Chemistry Research Institute, Xi’an 710065, China
‡Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry &
Materials Science, Northwest University, Xi’an 710127, China
S
* Supporting Information
ABSTRACT: In the presence of a carboxylic acid directing
group, Rh-catalyzed regioselective directed dialkylation of
B(4,5)−H bonds in o-carboranes and oxidative coupling with
allylic alcohols is reported. This strategy constructs a series of
4,5-dialkylated o-carboranes in good yields with excellent
regioselectivity. A possible catalytic cycle is proposed that
involves a tandem sequence of Rh-catalyzed cage B−H
activation, alkene insertion, selective β-H elimination, enol isomerization, and decarboxylation.
Scheme 1. Transition-Metal-Catalyzed Formation of Cage
B−C(sp), B−C(sp2), and B−C(sp3) Bonds in o-
Carboranes
arboranes, a class of three-dimensional compounds
1
Canalogous to benzene,
have unique properties which
have found many applications in medicine,2 in supra-
molecular design,3 and in coordination/organometallic
chemistry4 as well as in fluorescence/phosphorescence5 and
materials science.6 These intriguing properties and applica-
tions have drawn growing interest in the modification of
carboranes with diverse functional groups. In recent years,
transition-metal-catalyzed cage B−H activation for regiose-
lective boron functionalization of o-carboranes has emerged
as a powerful strategy and has resulted in many advance-
ments.7−10 However, the 10 B−H bonds of o-carboranes are
not fully equal because its unique structure makes the
functionalization difficult as the charge differences are very
small. For cage B−H where hydrogens are basic in o-
carboranes, electrophilic substitution reactions also proceed
stepwise in the order B(9,12) > B(8,10) > B(4,5,7,11) >
B(3,6).11 Therefore, selective and straightforward boron
substitution of o-carboranes is still a big challenge for
researchers.
To overcome this problem, directing groups are introduced
especially the use of −COOH as a weak coordinating
directing group for transition metal catalyzed B−H
activation.12 Carboxyl group can be easily introduced to the
cage carbon and removed after reactions. And it also was
proved to chelate the metal catalyst and stabilize the
metallacycle intermediates in such reactions.12a Over the
last several years, great achievements have been made by
Xie’s group to regioselective dehydrogenation of o-carborane
via transition metals.13 Besides that, they reported Pd-
catalyzed selective formation of cage B−C(sp)13d and B−
C(sp2)13a,c bonds by intermolecular cross-coupling of o-
carboranes (Scheme 1).
Generally, the oxidative Heck reaction can construct C−C
bond between aryl or alkenyl C−H bonds with olefins.14 To
solve the selective β-H elimination, Lei,15 Kommu,16 and
Jiang17 found selective arylation of electronically nonbiased
Received: August 23, 2019
© XXXX American Chemical Society
A
DOI: 10.1021/acs.orglett.9b03009
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
allylic alcohols through a redox-neutral pathway with
iodobenzene or oxidative coupling with benzoic acids,
respectively. Moreover, the oxidative coupling between
(hetero)arene and allyl alcohols provides an alternative
approach for C−H alkylation. Thus, this method can be
regarded as an efficient way to achieve alkylation of
unactivated arenes. Inspired by the aforementioned work,
we assume allylic alcohols can insert to the M−B bond to
develop a strategy of cage B−H alkylation through a
decarboxylative Heck-type reaction. On the other hand, our
groups also focus on the functionalization of o-carboranes.18
Herein, we report a Rh-catalyzed carboxylic acid directed
regioselective dialkylation of cage B−H bonds in o-carboranes
through oxidative Heck reaction.
Our investigation was initiated by using the reaction of 1-
COOH-2-nHex-C2B10H10 (1a) with but-3-en-2-ol (2a) in the
presence of 5 mol % of [Cp*RhCl2]2 and 2 equiv of AgOAc
in DCE at 90 °C for 18 h, B(4)-monoalkylated product 3a,
and B(4,5)-dialkylated product 4a were observed in 49% and
39% yields (Table 1, entry 1).13a Polar solvent DMF only
Table 2. Synthesis of cage B(4,5)-dialkylated o-
carboranes
a b
,
b
entry
R1
R2
yield (%)
1
2
3
4
5
6
7
8
nHex
nHex
nHex
nHex
nHex
nHex
nHex
nHex
nHex
nHex
nHex
nHex
nHex
nHex
nHex
nBu
Me
Et
Ph
80 (4a)
73 (4b)
77 (4c)
74 (4d)
72 (4e)
65 (4f)
81 (4g)
83 (4h)
35 (3i)
75 (4j)
66 (4k)
76 (4l)
70 (4m)
83 (4n)
64 (4o)
71 (4p)
trace
4-MeC6H4
3-MeC6H4
2-MeC6H4
4-tBuC6H4
3,5-Me2C6H3
4-MeOC6H4
2-naphthyl
4-FC6H4
4-ClC6H4
3-ClC6H4
4-BrC6H4
4-CF3C6H4
Me
c
9
10
11
12
13
14
15
16
a
Table 1. Optimization of Reaction Conditions
d
17
18
H
Ph
Me
Me
e
57 (4q)
b
a
entry
additive
solvent
temp (°C) 3a/4a (%)
Reaction conditions: 1 (0.1 mmol), 2 (2.4 equiv), [Cp*RhCl2]2 (5
mol %), AgOAc (4 equiv), 1,4-dixoane (1 mL, 0.1 M), in a closed
flask, 18 h. Isolated yields. Monoalkylated product was isolated, 4i
was detected less than 5% by GC. A trace amount of target product
was observed by GC. 90 °C, heated for 24 h.
1
2
3
4
5
6
7
8
9
2 equiv of AgOAc
2 equiv of AgOAc
2 equiv of AgOAc
2 equiv of AgOAc
4 equiv of AgOAc
4 equiv of Ag2CO3
4 equiv of Ag2O
4 equiv of Cu(OAc)2
4 equiv of AgOAc
4 equiv of AgOAc
DCE
DMF
90
90
90
90
90
90
90
90
70
70
49/39
−/−
b
c
d
toluene
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
52/37
42/55
18/82
30/68
28/72
22/45
5/95
e
were employed to couple with 1a. A methyl group on the
phenyl ring including para-substituted, meta-substituted, and
ortho-substituted 1-phenylprop-2-en-1-ols led to the corre-
sponding β-aryl ketones in moderate yields (Table 2, entries
4−6). Other electron-donating substituents such as 4-tBu and
3,5-Me2 afforded 4g and 4h in 81% and 83% yield,
respectively (Table 2, entries 7 and 8). However, for p-
methoxy-substituted substrate, only monoalkylated product
was isolated in a decreased yield of 35% (Table 2, entry 9).
2-Naphthyl-substituted product 4j also was obtained in 75%
yield (Table 2, entry 10). In addition, substrates bearing
halogen atoms such as F (4k), Cl (4l and 4m), and Br (4n)
were well tolerated. An electron-withdrawing group, −CF3,
on the phenyl ring also afforded the corresponding product in
64% yield (Table 2, entry 15). The effects of R1 on reaction
c
10
−/−
a
General reaction conditions: 1 (0.1 mmol), 2a (2.4 equiv),
[Cp*RhCl2]2 (5 mol %), solvent (1.0 mL, 0.1 M), in a closed flask,
b
c
18 h. GC yields of product 3a and 4a; o-Carborane was the major
product; [Cp*IrCl2]2 was used as catalyst.
gave the decarboxylation product, and o-carborane (Table 1,
entry 2) and toluene resulted in lower yields (Table 1, entry
3). To our delight, 1,4-dixoane gave better yields of 3a and
4a (entry 4). Increasing the amount of AgOAc to 4 equiv led
to a higher selectivity of 4a (Table 1, entry 5). After that,
different additives such as Ag2CO3, Ag2O, and Cu(OAc)2 did
not give better results (Table 1, entries 6−8). Lowering the
reaction temperature resulted in higher molar ratios of 3a/4a
(Table 1, entry 9). Next, Ir(III) complexes were also checked
but showed a poor catalytic activity in this reaction (Table 1,
entry 10). In view of reaction efficiency and selectivity of 4a,
entry 9 in Table 1 was chosen as the optimal reaction
condition.
n
results were also examined. For R1 = Bu, the corresponding
product 4p was obtained in 71% isolated yield (Table 2,
entry 16). If R1 = H, only a trace product was observed from
GC−MS, owing to its sensitive electronic effects to this
reaction (Table 2, entry 17). If R1 = Ph, 4q was obtained in
57% isolated yield (Table 2, entry 18). To our disappoint-
ment, nonterminal allylic alcohols were not suitable for this
transformation.
1
Compounds 4 were fully characterized by H, 13C, and 11B
Under the optimized reaction conditions, we investigated
the reaction scope. As shown in Table 2, the alkyl-substituted
allyl alcohols were suitable substrates for this transformation
and gave the corresponding products in good yields (Table 2,
entries 1 and 2). Then various aryl-substituted allylic alcohols
NMR spectroscopy as well as high-resolution mass spectrom-
etry. The molecular structure of 4p was further confirmed by
single-crystal X-ray analyses and shown in Figure 1.
On the basis of the above results, a possible reaction
mechanism for the Rh-catalyzed oxidative coupling reaction
B
DOI: 10.1021/acs.orglett.9b03009
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
elimination in Rh-catalyzed oxidative Heck reaction of
electronically nonbiased olefins.
ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.or-
glett.9b03009.
Experimental procedures and compound character-
ization (PDF)
Figure 1. Solid-state molecular structure of 4p.
Accession Codes
between 1-COOH-2-R-C2B10H10 and allylic alcohols through
selective β-H elimination is proposed (Scheme 2). First,
CCDC 1946500 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
via www.ccdc.cam.ac.uk/data_request/cif, or by emailing
data_request@ccdc.cam.ac.uk, or by contacting The Cam-
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
Scheme 2. Proposed Reaction Mechanism
AUTHOR INFORMATION
■
Corresponding Author
*E-mail: lujian204@gmail.com.
ORCID
Ling Zhou: 0000-0002-6805-2961
Jian Lu: 0000-0001-5418-3197
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by the National Natural Science
Foundation of China (Grant No. 21905223) and the China
Postdoctoral Science Foundation (Grant No. 2019M653783).
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DOI: 10.1021/acs.orglett.9b03009
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