Lithium compounds as single site catalysts for hydroboration of alkenes and alkynes

Article abstract of DOI:10.1039/c9cc05783h

The hydroboration of alkenes and alkynes using easily accessible lithium compounds [2,6-di-tert-butyl phenolatelithium (1a) and 1,1′ dilithioferrocene (1b)] has been achieved with good yields, high functional group tolerance and excellent chemoselectivity

Full text of DOI:10.1039/c9cc05783h

View Article Online
View Journal
ChemComm
Chemical Communications
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: M. K. Bisai, S.
Yadav, T. Das, K. Vanka and S. S. Sen, Chem. Commun., 2019, DOI: 10.1039/C9CC05783H.
Volume 54
Number
January 2018
Pages 1-112
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
1
4
ChemComm
Chemical Communications
rsc.li/chemcomm
Accepted Manuscripts are published online shortly after acceptance,
before technical editing, formatting and proof reading. Using this free
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes to the
text and/or graphics, which may alter content. The journal’s standard
Terms & Conditions and the Ethical guidelines still apply. In no event
shall the Royal Society of Chemistry be held responsible for any errors
or omissions in this Accepted Manuscript or any consequences arising
from the use of any information it contains.
ISSN 1359-7345
COMMUNICATION
S. J. Connon, M. O. Senge et al.
Conformational control of nonplanar free base porphyrins:
towards bifunctional catalysts of tunable basicity
rsc.li/chemcomm

Page 1 of 4
Please d oC hn eo mt Ca do mj u ms t margins
View Article Online
DOI: 10.1039/C9CC05783H
ChemComm
COMMUNICATION
Lithium compounds as single site catalysts for hydroboration of
alkenes and alkynes
ab
ab
bc
bc
ab
Milan Kumar Bisai, Sandeep Yadav, Tamal Das, Kumar Vanka, and Sakya S. Sen*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
The hydroboration of alkenes and alkynes using easily accessible equilibrium like group 2 elements. Moreover, as most of the
lithium compounds [2,6-ditertbutyl phenolatelithium (1a) and 1,1' main group catalysts are frequently prepared from the
dilithioferrocene (1b)] have been achieved with good yields, high corresponding lithium reagents, taking advantage of the direct
functional group tolerance and excellent chemoselectivity. use of lithium compounds in catalysis, would obviate the need
Deuterium-labeling experiments confirm the cis-addition of for such additional transformations. In fact, the group of Mulvey
pinacolborane. The methodology has been further extended to demonstrated the use of lithium aluminates as catalysts for the
2
7,28
myrcene, which undergoes selective 4,3- hydroboration. DFT hydroboration of aldehydes, ketones, and imines,
and the
calculations provide insights into the mechanism.
group of Cowley and Thomas used LiAlH for the hydroboration
of alkenes, but it was aluminum which is the active catalyst in
both these cases and lithium only influences the reactivity. This
4
2
3
Hydroboration of functionalized alkynes and alkenes using
1
excess pinacolborane (HBpin) is known, but their catalytic
was confirmed by using AlEt
3
(a surrogate of AlH
3
) as a single
2
conversion usually requires a late transition metal catalyst.
site catalyst to accomplish the hydroboration.
Recently, the demand for supplanting the transition metal
catalysts by more earth abundant and less toxic main group
surrogates is ever increasing. Hydroboration using compounds
with group 2 elements has been limited tothe catalytic
reduction of unsaturated polar bonds, such as aldehydes,
OLi·THF
H
Bpin
R2
Li
R1
1a/1b (2-8 mol%)
Toluene, 100 oC,
tBu
tBu
R2 + H-Bpin
Fe
TMEDA
Li
R1= alkyl/aryl
2
R1
12-18 h
R =H/alkyl/aryl
1a
1b
Catalysts
3
-14
ketones, imines, amides, esters etc.
Although compounds
Scheme 1. Lithium compound catalyzed hydroboration of alkene and alkynes.
with p-block elements are emerging as proficient catalysts for
alkyne1 and alkene
5-20
21-23
hydroboration, there are very limited
Hence, the utilization of lithium compounds as catalysts has
been largely neglected. It is only recently that the groups of
Okuda, Mulvey and others have started to use lithium
compounds as single site catalysts for hydroboration of
Recently, n-BuLi was shown as an
efficient catalyst for the hydroboration of alkynes with HBpin.
However, the substrate scope of the methodology was limited,
and the mechanism was not elaborated. Thus, there remains a
need for the development of alkene and alkyne hydroboration
with lithium compounds as single site catalysts. Last year, we
have reported the hydroboration and cyanosilylation of a range
of aldehydes and ketones using 2,6-ditert-butyl phenolate
lithium (1a), and 1,1'-dilithioferrocene (1b), and
reports on s-block metal catalyzed alkene or alkyne
hydroboration. While Rueping and coworkers reported the first
magnesium catalyzed hydroboration of terminal and internal
alkynes,24 the group of Parkin demonstrated styrene
2
9-33
aldehydes and ketones.
2
5
hydroboration by a terminal magnesium hydride. Besides,
Zhao and co-workers reported the hydroboration of carbonyl
groups and styrene substrates using NaOH powder, although
3
4
2
6
the scope of styrene substrates was somewhat limited.
The advantages of using lithium compounds are (i) cheap,
ii) moderately abundant (65 ppm in the Earth’s crust), (iii)
(
readily accessible, and (iv) they do not involve in Schlenk
[
2
Dipp nacnac]Li·THF (1c) and compared how the
a. Inorganic Chemistry and Catalysis Division, CSIR-National Chemical Laboratory,
Dr.Homi Bhabha Road, Pashan, Pune 411008, India. E-mail: ss.sen@ncl.res.in
electronegativity of ligand associated with the Li center
influences the catalytic activity. The reason to select 1b over
monolithiated ferrocene can be attributed to more to sterics of
the former as well as the ease of synthesis (monolithiated
ferrocene preparation usually needs tBuLi, while 1b can be
b.
32
Academy of Scientific and Innovative Research (AcSIR), Ghaziabad-201002, India.
Physical and Material Chemistry Division, CSIR-National Chemical Laboratory, Dr.
c.
Homi Bhabha Road, Pashan, Pune 411008, India.
Electronic Supplementary Information (ESI) available: Experimental details,
theoretical calculations, kinetic analysis and representative NMR spectra.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Please d oC hn eo mt Ca do mj u ms t margins
Page 2 of 4
COMMUNICATION
ChemComm
prepared from nBuLi).35 Although these compounds are comparison purpose, cyclopentadienyllithium Vie(wCpArLtiic)le Ownlianes
prepared from alkyllithium reagents, they are solid in nature, employed as the catalyst. With 2.0 mol%DOcIa: 1t0a.l1y0s3t9l/oCa9dCiCn0g57C8p3LHi
easy to handle, and stable under inert conditions for a long afforded 65% yield under the same reaction condition for the
time. Herein, we report efficient hydroboration of more hydroboration of phenylacetylene (See Supporting Information,
challenging alkenes and alkynes by 1a and 1b (Scheme 1). Only Table S3, entry 6). Slightly higher catalyst loading (4.0 mol% for
trace amount of conversion was observed when 1c was used as 1b and 8.0 mol% for 1a) and time (18 h) are required for
the catalyst.
hydroboration of alkenes. Both aliphatic and aromatic
alkene/alkynes underwent hydroboration to form the
corresponding alkyl or vinyl-boronates in good to excellent
yields (Scheme 2 and Scheme 3), reflecting the high efficiency
of the catalysts.
Smooth hydroboration of different aromatic alkenes or
alkynes with electron donating or withdrawing substituents at
o/m/p position was observed. Both catalysts tolerate functional
groups such as halogens (2f, 2o, 2p, 3d, and 3h), alkoxy (2d, 2e,
H
H
H
H
Bpin
Bpin
Bpin
Bpin
Me
Bpin
Bpin
Bpin
Bpin
Bpin
Bpin
Me
MeO
2a
2b
2c
2d
2a% (99:1)
9b% (95:5)
97a% (99:1)
96b% (98:2)
88a% (99:1)
86b% (98:2)
H
92a% (98:2)
93b% (95:5)
H
9
8
H
H
Bpin
Cl
tBuO
2e
2f
2g
2h
1a% (98:2)
5b% (98:2)
81a% (97:3)
59b% (98:2)
90a% (99:1)
82b% (96:4)
65a% (99:1)
62b% (94:6)
8
8
3
b, and 3i), heterocycle (3k), amino (3f) containing substrates.
H
H
Ph
Me
H
H
Bpin
However, in addition to alkyne hydroboration, lithium-halide
exchange was also observed for 3e in 29% yield. The lithium
halide exchange was more pronounced for 3m as the
metathesis product was obtained in more than 70% yield.
Intramolecular chemoselective hydroboration of alkyne over
alkene was observed for 3j. In contrast to terminal alkynes,
internal alkynes (3n, 3o, and 3p) form their corresponding
boronates in moderate yields under the optimization
conditions. However, similar to Rueping's magnesium catalyst,
by increasing the catalyst loading (5 mol%) and reaction time
Ph
2
i
2j
2k
2l
7
7
3a% (97:3)
4b% (95:5)
H
87a% (95:5)
58a% (99:1)
65a% (98:2)
65b% (99:1)
51b% (99:1)
68b% (99:1)
H
H
Bpin
Bpin
Bpin
Bpin
3
H
Br
Br
2m
2n
2o
2p
87a% (99:1)
65b% (98:2)
69a% (99:1)
66b% (99:1)
9
9
3a% (98:2)
6b% (99:1)
92a% (100)
64b% (100)
Scheme 2 Hydroboration Scope with alkene substrates. Reaction conditions: Alkene
0.50 mmol), HBpin (0.55 mmol, 1.1equiv), 4.0-8.0 mol% catalyst, 18 h reaction at 100 °C
temperature in neat or in toluene. Yields were determined by the H NMR integration
(
1
relative to mesitylene. Henceforth superscripts a and b stand for the catalysts 1a and 1b (36 h), good yields are achieved for 3o (80%). We have also
respectively. Ratios in parentheses report the distribution of regioisomers (linear vs tested unsymmetrical alkyne, phenylpropyne for hydroboration
branched).
which afforded a mixture of α- and β-vinyl boranates (3p) in 2:3
and 3:7 ratio for 1a and 1b, respectively. Aliphatic alkenes (2m-
H
H
H
H
Bpin
Bpin
Bpin
F
Bpin
2p) or alkynes (3l-3n) were effectively converted to their
corresponding products. Increase of sterics has little effect on
the yield as seen in the cases of hydroboration of 2h, 2k, 3n, and
H
H
H
H
MeO
tBu
3
a
3b
3c
3d
a
a
a
a
9
2 % (100:0)
0b% (100:0)
H
96 % (100:0)
87 % (100:0)
67 % (100:0)
b
b
b
9
84 % (100:0)
89 % (100:0)
66 % (100:0)
3
o.
Cl
H
H
H
Bpin
Bpin
Bpin
Bpin
CH3
CH3
CH2
H
H
H
H
H
CH3
Me2N
Me
F
H3C
3e
3f
3g
3h
a
a
a
a
5
5 % (100:0)
1b% (100:0)
84 % (100:0)
94 % (100:0)
73 % (100:0)
b
b
b
Bpin
5
86 % (100:0)
86 % (100:0)
80 % (100:0)
H
H
H
H
H
H
Bpin
Bpin
H
CH3
CH3 H3C
CH3
Bpin
Bpin
Bpin
Bpin
Me
Bpin
4
a
4b
4c
4d
a b
5
a
b
a
b
1
2 /18
13 /15
73a/65b
61 /63
H
H
H
H
S
MeO
Br
3
i
3j
3k
3l
a
a
a
81a% (100:0)
84b% (100:0)
8
8 % (100:0)
0b% (100:0)
97 % (100:0)
75 % (100:0)
Scheme 4. Selective alkene hydroboration for terpenes.
b
b
9
94 % (100:0)
64 % (100:0)
H
H
H
H
Bpin
Bpin
Bpin
Bpin
CH3
Et
To further explore the catalytic potential of 1a and 1b,
naturally occurring terpenes have been chosen for the selective
hydroboration of the olefinic bond. Although poor yields were
obtained for R- or S- limonene (4a and 4b), myrcene (4c) and β-
pinene (4d) were converted to the corresponding alkyl
boronate ester in good yield with excellent selectivity.
Interestingly, 4,3-selective hydroboration of 2-substituted 1,3-
diene (4c) was observed for both the catalysts. Note that,
hydroboration of dienes to access allylboranes is less-
H
Et
Ph
3
m
3n
3o
3p
a
a
a
a
2
0 % (100:0)
2b% (100:0)
47 % (100:0)
53 % (100:0)
58+37 % (61:39)
b
b
b
1
50 % (100:0)
57 % (100:0)
40+18 % (69:31)
Scheme 3 Scope of hydroboration with alkyne substrates. Reaction conditions: Alkyne
0.50 mmol), HBpin (0.55 mmol, 1.1 equiv), 2.0 mol% catalyst, 12 h reaction at 100 °C in
toluene. Yields were determined by the H NMR integration relative to mesitylene.
(
1
A brief screening of catalyst loading, temperature and time
has been carried out for the hydroboration of styrene or
phenylacetylene with 1.1 equivalent of HBpin (See Supporting
Information, Table S1 and S3) to achieve the best conversion.
For hydroboration of alkynes, catalyst loadings are 2.0 mol%
and the reactions were over around 12 h when heated at 100
3
6
established, and only known with transition metals such as Fe,
3
7
38
39
Co, Ni, Ir, etc. This is the first report of a main group
element catalyzed selective hydroboration of myrcene.
Deuterium labelling experiments were carried out for the
catalytic hydroboration of alkyne to understand the
°
C. Note that, the catalyst loading is substantially lesser than
nBuLi (10 mol%) catalyzed alkyne hydroboration. For
2
3
5
stereoselectivity. A sharp resonance at δ 6.18 ppm in the H
2
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 4
Please d oC hn eo mt Ca do mj u ms t margins
ChemComm
NMR for the catalytic reduction of PhC≡CD with HBpin
COMMUNICATION
Full quantum chemical calculations were doneViwewitAhrtidcleenOnsliitnye
designates a cis configuration of the deuterium and phenyl ring functional theory (DFT) at the dispersionDaOnI:d10s.o10lv3e9n/Ct9cCoCr0re57c8te3Hd
[
(a), Scheme 5]. Similarly, the cis arrangement of deuterium and PBE/TZVP level of theory in order to understand the mechanism
the Bpin moiety was confirmed from the resonance at δ 7.28 (Scheme 7 and Scheme 8) of the alkene and alkyne
2
ppm in the H NMR spectrum for the catalytic reaction of hydroboration reaction in the presence of 1a. [please see the
PhC≡CH and DBpin [(b), Scheme 5]. This experiment attests a cis Supporting Information, Figures 81 and 82 for further details].
stereoselectivity, which is in good agreement with ScOTf
OLi
Ph
H
tBu
tBu
Li+
H
O
Me
Me
Me
Me
mediated alkyne hydroboration, reported by Geetharani and
coworkers.40 Intermolecular chemoselective hydroboration of
aldehydes, alkene and alkyne were also studied in three
different sets of the reactions and the results are summarized
in Scheme 6.
B
H
H-Bpin
tBu
O
O
Bpin Pdt
(
-28.5)
tBu
X
Int-2
(15.2)
Ph
H
H
B
O
H
O
Me
Me
Me
Me
Me
Me
Me
B
D
Li
O
O
tBu
Li
O
Bpin
1
a/1b (2.0 mol%)
Toluene (0.75 mL)
00 C, 12 h
tBu
O
+
HBpin
Me
a)
D
tBu
tBu
H
1
TS-1
35.4)
(
‡
Int-1
-0.7)
H
G =35.4
(
Bpin
1
a/1b (2.0 mol%)
Toluene (0.75 mL)
00 C, 12 h
Ph
b)
H
+
DBpin
D
H
1
Scheme 7. The catalytic cycle and reaction mechanism for the alkyne hydroboration by
catalyst 1a, calculated at the PBE/TZVP level of theory with DFT. The relative free energy
(
Scheme 5. Deuterium labelling experiment: (a) Hydroboration of phenylacetylene-D with
HBpin. (b) Hydroboration of phenylacetylene with DBpin.
∆G) for each species are shown within the parenthesis of the catalytic cycle. ΔG‡
represent the Gibbs free energy of activation respectively. All values are in kcal/mol.
H
1
a/1b (2.0 mol%)
Bpin
O
HBpin (1.0 equiv)
OBpin
+
+
(1)
(2)
(3)
OLi
Toluene (0.5 mL)
rt, 12 h
H
Ph
H
tBu
tBu
6a/92b
0a/0b
H
H
9
H
H
H
Bpin Pdt
1
a/1b (2.0 mol%)
Bpin
Bpin
Bpin
(-9.1)
H
O
B
Me
Me
HBpin (1.0 equiv)
+
+
+
Toluene (0.5 mL)
H
H
Li
O
Ph
O
Me
Me
1
00 C, 12 h
6a/72b
a
b
7
14 /18
tBu
tBu
H
H
O
Me
Me
Me
B
1
a/1b (4.0-8.0 mol%)
HBpin (2.0 equiv)
Li
Bpin
O
Int-1
(-0.7)
O
+
tBu
tBu
Me
Toluene (0.5 mL)
1
00 C, 18 h
8a/91b
a
b
9
74 /70
H
TS-1
37.1)
H
(
Ph
H
Scheme 6. Competitive experiment for chemoselective hydroboration.
Scheme 8. The catalytic cycle and reaction mechanism for the alkene hydroboration by
catalyst 1a.
1
No appreciable changes in the H NMR was observed from
the stoichiometric reaction of 1a with styrene or
phenylacetylene, even after heating at 100 °C overnight.
In the first step of the reaction, a weakly coordinating
However, the reaction between 1a and HBpin in toluene-d
8
complex (Int-1) is formed between catalyst 1a and HBpin, with
shows a new set of resonance in the B NMR at δ 4.7 ppm, one of the oxygen atoms of pinacolborane approaching towards
1
1
3
2,41
indicating the formation of an intermediate (Int-1)
along the lithium atom of 1a. The reaction energy (ΔE) and the Gibbs
with a singlet at δ 21.6 and a quintet at –39.8 ppm for the free energy (ΔG) for this step are -11.5 kcal/mol and -0.7
˗
formation of a trialkoxyborane [2,6-tBu
2
-C
6 3
H
-OBpin] and BH
4
kcal/mol respectively. Another possibility of coordinating
anion, respectively. In addition, a singlet at δ 86.9 and a quartet phenolate oxygen to boron atom of pinacolborane leading to a
at -25.4 ppm were also observed, probably due to the four-coordinate boron complex (Int-2) was found to be
4
2
decomposition of HBpin and Lewis base·BH
3
adduct. A white thermodynamically unfavorable due to high ΔG (15.2 Kcal/mol)
precipitate is formed in the NMR tube after 3-4 h and the filtrate of the reaction. Following this, the alkene or alkyne substrate
part shows only three peaks at δ 4.7, 21.6 and -39.8 ppm in the approaches towards the B-H bond of Int-1. This is the overture
1
1
B NMR spectrum (see Supporting Information, Scheme S8). to the nucleophilic attack by the C-C double or triple bond of
The elimination of LiH could lead to the formation of both alkene or alkyne to the boron centre of the HBpin, with the
4
3
trialkoxyborane and LiBH
4
.
However, due to the very high hydride being transferred from the boron centre to the alkene
lattice energy and poor solubility, the involvement of LiH in the or alkyne carbon centre having minimum hydrogen. This occurs
catalytic activity is very unlikely, which was also noted by the through a four-membered transition state (TS-1)/(TS-1ꞌ) and
groups of Mulvey,33 Thomas, and Cowley. No conclusive NMR leads to the hydroboration product (Pdt-1)/(Pdt-1ꞌ) along with
spectra were obtained from the stoichiometric reactions the regeneration of the catalyst. The ΔE (-32.8 kcal/mol and -
23
between 1b and HBpin and always peak broadening was 11.9 kcal/mol) and ΔG (-28.5 kcal/mol and -9.1 kcal/mol) values
‡
observed.
for these steps are highly negative and the barriers (ΔG s)
corresponding to the transition states are moderate: 35.4
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please d oC hn eo mt Ca do mj u ms t margins
Page 4 of 4
COMMUNICATION
ChemComm
Technol., 2019, 9, 3307-3336; (b) C. C. Chong andViRew. KAritnicjloe ,OAnlCinSe
kcal/mol and 37.8 kcal/mol for the alkyne and alkene
respectively. The moderate barriers explain the delicate
feasibility of the reaction at 100 °C. In the transition states,
there is a significant amount of B-H bond activation (1.27 Å vs
Catal., 2015, 5, 3238–3259.
DOI: 10.1039/C9CC05783H
1
1
1
1
1
5 Z. Yang, M. Zhong, X. Ma, K. Nijesh, S. De, P. Parameswaran
and H. W. Roesky, J. Am. Chem. Soc., 2016, 138, 2548–2551.
6 A. Bismuto, S. P. Thomas and M. J. Cowley, Angew. Chem. Int.
Ed., 2016, 55, 15356–15359.
7 J. S. McGough, S. M. Butler, I. A. Cade and M. J. Ingleson,
Chem. Sci., 2016, 7, 3384–3389.
1
.19 Å in the intermediate complex) occurs, which allows the
hydride transfer from the boron to the alkene or alkyne carbon
centre, along with the simultaneous C-C double and triple bond
cleavage and B-O bond formation.
8 M. Fleige, J. Möbus, T. v. Stein, F. Glorius and D. W. Stephan,
Chem. Commun.,2016, 52, 10830−10833.
Here we are unwavering the utility of very simple, cost
effective and almost non-toxic lithium compounds (1a and 1b)
for the catalytic hydroboration of a range of alkenes and alkynes
including conjugated terpenes. Chemoselectivity as well as
regioselectivity for the described catalytic process have been
investigated. DFT calculations reveal that the role of the Li
compounds could be interpreted as sterically demanding Lewis
acids which bind to one of the Lewis basic O atoms of HBpin,
and thereby setting up a platform for the HBpin to offer its B-H
bond to the unsaturated alkene and alkyne.
9 (a) J. R. Lawson, L. C. Wilkins and R. L. Melen, Chem. Eur. J.,
2017, 23, 10997−11000; (b) J. L. Carden, L. J. Gierlichs, D. F.
Wass, D. L. Browne and R. L. Melen, Chem. Commun., 2019,
5
5, 318–321.
0 D. Franz, L. Sirtl, A. Pöthig and S. Inoue, Z. Anorg. Allg. Chem.,
016, 642, 1245–1250.
2
2
2
2
1 Q. Yin, S. Kemper, H. F. T. Klare and M. Oestreich, Chem. Eur.
J., 2016, 22, 13840−13844.
2 A. Prokofjevs, A. Boussonnihre, L. Li, H. Bonin, E. Lacite, D. P.
Curran and E. Vedejs, J. Am. Chem. Soc., 2012, 134, 12281–
1
2288.
3 A. Bismuto, M. J. Cowley and S. P. Thomas, ACS Catal., 2018,
, 2001–2005.
2
Science and Engineering Research Board (SERB), India
8
(
CRG/2018/000287) (SSS), and (EMR/2014/000013) (KV) is 24 M. Magre, B. Maity, A. Falconnet, L. Cavallo and M. Rueping,
Angew. Chem., Int. Ed., 2019, 58, 7025–7029.
acknowledged for providing financial assistance. MKB, SY, and
TD thank CSIR, India for the research fellowships.
2
2
2
5 M. Rauch, S. Ruccolo and G. Parkin, J. Am. Chem. Soc., 2017,
1
39, 13264–13267.
6 Y. Wu, C. Shan, J. Ying, J. Su, J. Zhu, L. L. Liu and Y. Zhao, Green
Chem., 2017, 19, 4169−4175.
Conflicts of interest
There are no conflicts to declare.
7 V. A. Pollard, M. A. Fuentes, A. R. Kennedy, R. McLellan and
R. E. Mulvey, Angew. Chem., Int. Ed., 2018, 57,
1
0651−10655.
2
8 L. E. Lemmerz, R. McLellan, N. R. Judge, A. R. Kennedy, S. A.
Orr, M. Uzelac, E. Hevia, S. D. Robertson, J. Okuda and R. E.
Mulvey, Chem. Eur. J., 2018, 24, 9940–9948.
Notes and references
2
3
3
3
3
3
3
9 D. Mukherjee, H. Osseili, T. P. Spaniol and J. Okuda, J. Am.
Chem. Soc., 2016, 138, 10790–10793.
0 H. Osseili, D. Mukherjee, K. Beckerle, T. P. Spaniol and J.
Okuda, Organometallics, 2017, 36, 3029–3034.
1
C. E. Tucker, J. Davidson and P. Knochel, J. Org. Chem., 1992,
5
7, 3483–3485.
2
For reviews on transition metal catalyzed hydroboration: (a) I.
Beletskaya and A. Pelter, Tetrahedron, 1997, 53, 4957–5026;
1 H. Osseili, D. Mukherjee, T. P. Spaniol and J. Okuda, Chem. Eur.
J., 2017, 23, 14292–14298.
(
b) N. Miyaura in Catalytic Heterofunctionalization (Eds: A.
Togni, H. Grützmacher), Wiley-VCH, Weinhein, 2001, pp. 1–
2 M. K. Bisai, T. Das, K. Vanka and S. S. Sen, Chem. Commun.,
4
2
6; (c) C. M. Vogels and S. W. Westcott, Curr. Org. Chem.,
005, 9, 687–699.
2
018, 54, 6843–6846.
3 R. McLellan, A. R. Kennedy, R. E. Mulvey, S. A. Orr and S. D.
Robertson, Chem. Eur. J., 2017, 23, 16853–16861.
3
4
5
6
7
8
9
M. Arrowsmith, T. J. Hadlington, M. S. Hill and G. Kociok-Köhn,
Chem. Commun., 2012, 48, 4567–4569.
M. Arrowsmith, M. S. Hill and G. Kociok-Köhn, Chem. Eur. J.,
4 D. Yan, X. Wu, J. Xiao, Z. Zhu, X. Xu, X. Bao, Y. Yao, Q. Shen and
M. Xue, Org. Chem. Front., 2019, 6, 648–653.
2
013, 19, 2776−2783.
5 S. Bruña, A. Mª González-Vadillo, M. Ferrández, J. Perles, M.
M. Montero-Campillo, O. Mób and I. Cuadrado, Dalton Trans.,
C. Weetman, M. S. Hill and M. F. Mahon, Chem. Commun.,
015, 51, 14477–14480.
K. Manna, P. Ji, F. X. Greene and W. Lin, J. Am. Chem. Soc.,
016, 138, 7488–7491.
2
2
017, 46, 11584–11597.
6 J. Y. Yu. B. Moreau and T. Ritter, J. Am. Chem. Soc., 2009, 131,
2915–12917.
7 R. J. Ely and J. P. Morken, J. Am. Chem. Soc., 2010, 132,
534−2535.
8 J. V. Obligacion and P. J. Chirik, J. Am. Chem. Soc., 2013, 135,
9107−19110.
3
3
3
2
1
D. Mukherjee, S. Shirase, T. P. Spaniol, K. Mashima and J.
Okuda, Chem. Commun., 2016, 52, 13155–13158.
L. Fohlmeister and A. Stasch, Chem. Eur. J., 2016, 22, 10235–
2
1
0246.
1
C. Weetman, M. D. Anker, M. Arrowsmith, M. S. Hill, G.
3
4
9 D. Fiorito and C. Mazet, ACS Catal., 2018, 8, 9382−9387.
0 S. Mandal, P. K. Verma and K. Geetharani, Chem. Commun.,
Kociok-Köhn, D. J. Liptrot and M. F. Mahon, Chem. Sci., 2016,
7
, 628–641.
2
018, 54, 13690-13693.
1
1
1
1
1
0 S. Yadav, S. S. Pahar and S. S. Sen, Chem. Commun., 2017, 53,
562–4564.
4
4
4
1 (a) A. Bonet, H. Gulyás and E. Fernández, Angew. Chem., Int.
Ed., 2010, 49, 5130–5134; (b) R. Dasgupta, S. Das, S. Hiwase,
S. Pati and S. Khan, Organometallics, 2019, 38, 1429–1435.
2 K. Burgess, W. A. vander Donk, S. A. Westcott, T. B. Marder,
R. T. Baker and J. C. Calabrese, J. Am. Chem. Soc., 1992, 114,
4
1 S. Yadav, R. Dixit, M. K. Bisai, K. Vanka and S. S. Sen,
Organometallics, 2018, 37, 4576-4584.
2 D. Mukherjee, A. Ellern and A. D. Sadow, Chem. Sci., 2014, 5,
9
59–964.
9
350-9359.
3 N. L. Lampland, M. Hovey, D. Mukherjee and A. D. Sadow, ACS
Catal., 2015, 5, 4219–4226.
3 I. P. Query, P. A. Squier, E. M. Larson, N. A. Isley and T. B. Clark,
J. Org. Chem., 2011, 76, 6452–6456.
4 For reviews on main group compound carbonyl
hydroboration, see: (a) M. L. Shegavi and S. K. Bose, Catal. Sci.
4
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins