Iron Catalyzed Hydroboration of Aldehydes and Ketones

Article abstract of DOI:10.1021/acs.joc.7b02020

We report an operationally convenient room temperature hydroboration of aldehydes and ketones employing Fe(acac)₃ as precatalyst. The hydroboration of aldehydes and ketones proceeded efficiently at room temperature to yield, after work up, 1° and 2° alcohols; chemoselective hydroboration of aldehydes over ketones is attained under these conditions. We propose a σ-bond metathesis mechanism in which an Fe-H intermediate is postulated to be a key reactive species.

Full text of DOI:10.1021/acs.joc.7b02020

Subscriber access provided by READING UNIV
Note
Iron catalyzed hydroboration of aldehydes and ketones
Sem Raj Tamang, and Michael Findlater
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.7b02020 • Publication Date (Web): 30 Oct 2017
Downloaded from http://pubs.acs.org on October 30, 2017
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts
appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered
to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just
Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
The Journal of Organic Chemistry is published by the American Chemical Society.
1155 Sixteenth Street N.W., Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 8
The Journal of Organic Chemistry
1
2
3
4
5
6
Iron catalyzed hydroboration of aldehydes and ketones
7
8
Sem Raj Tamang and Michael Findlater*
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Department of Chemistry and Biochemistry, Texas Tech. University, Lubbock, TX 79409
Supporting Information Placeholder
Hydroboration of carbonyl compounds into their respective al-
ABSTRACT: We report an operationally convenient
room temperature hydroboration of aldehydes and ke-
tones employing Fe(acac)3 as precatalyst. The hydrobo-
ration of aldehydes and ketones proceeded efficiently at
room temperature to yield, after work up, 1° and 2° al-
cohols; chemoselective hydroboration of aldehydes over
ketones is attained under these conditions. We propose a
sigma bond metathesis mechanism in which an Fe-H
intermediate is postulated to be a key reactive species.
cohols (1° and 2°) is also an important transformation in organic
chemistry.15a, 21 While this reaction has been effectively studied
using precious metals,22 complexes containing first row transi-
tion metals (Cu,23 Mn,24 Ti25 and Zn26), main group elements
(Ca,27 Mg, 28 Al,29 Sn,30 Ge,30 P,22b Ga,31 and Ge32) and even lan-
thanides33 have been developed. Herein, we wish to report the
first example of an operationally simple Fe-catalyzed hydrobora-
tion system, capable of converting aldehydes and ketones to bo-
ronic esters at room temperature.
Scheme 1. Model hydroboration catalysis of 1a
A wide variety of transition metal elements are now employed in
catalyzing the transformations of organic substrates.1 Precious
metals have come to dominate this field; recently there has been
a surge of interest in catalysts based upon first row metal ele-
ments.2 This interest is driven by the demands for efficient,
cheap, and atom economic chemical transformations. However,
the shift from precious to abundant metal catalysis is still in its
infancy; earth abundant transition metal catalyzed transfor-
mations are yet to be fully understood from both mechanistic and
conceptual perspectives. Nonetheless, reactions that were once
typically limited to precious metals: arylation,3 alkylation,4
alkenylation,5 hydrosilylation,6 borylation,7 amination,8 and oxi-
dation9 have now been reported employing earth abundant metal
replacements.10, 2c
Initially, we examined the catalytic hydroboration of 4’-
methylacetophenone (1a) with pinacolborane (HBPin). The reac-
tion of 1a with HBPin in THF employing Fe(acac)3 (3a) for 24
hrs afforded only 10 % of reduced product. However, we were
delighted to observe the formation of a highly reactive catalytic
species upon addition of NaHBEt3 to 3a; the color of the solution
changed from red to dark brown upon salt addition. Thus, stir-
ring 1a and HBPin (1.5 equiv.) at room temperature for 10 hrs,
after pre-activation of 3a, resulted in 72 % yield of the desired
alcohol product (2a). After 24 hrs of stirring, yields of up to 84
% of 2a could be obtained. The effectiveness of the catalyst was
not affected when the filtrate (after filtration of the activated
catalyst) was used; 82 % of 2a was afforded after 24 hrs of stir-
ring. Thus, the presence of a homogeneous catalyst is strongly
implied. Moreover, evacuating the volatiles upon activation in
vacuo at 45 C for 1hr prior to catalysis did not affect activity
either; 84 % of 2a was afforded after 24 hrs of stirring. When the
reaction mixture was heated at 50 ⁰C for 1hr, 100 % conversion
of 4’-methylacetophenone was observed based on TLC analysis.
However, we decided to focus upon the exploration of opera-
tionally convenient catalytic conditions and chose to pursue all
further reactions at room temperature. The catalytic loading of
3a could be reduced to 1 mol % but resulted in only 59 % yield
of 2a after 24hrs at room temperature. It should be noted that
Efforts to incorporate earth abundant transition metals in catalyt-
ic hydroboration have been driven by the key role organoborates
play in organic chemistry as synthetic surrogates. A number of
catalytic methods have been employed in the synthesis of alkyl
and vinyl boronates.11 Metal catalyzed olefin hydroboration us-
ing catecholborane and pinacolborane have been widely reported
with precious metal complexes (Rh,11b, 12 Ru,13 and Ir12b, 12h, 14).
These systems have shown remarkable functional group toler-
ance, excellent regioselectivity, and enantioselectivity.11b, 11e, 15a,
12f, 12g, 15b
The importance of organoborates has spurred progress in Fe and
Co catalyzed hydroboration of olefins. Chirik et. al. reported
anti-Markovnikov selective hydroboration of olefins catalyzed
by bis(imino)pyridine complexes of Fe16 and Co.17 Huang and
coworkers reported Fe18 and Co19 complexes supported by PNN
ligands with varying R groups (R = t-Bu, i-Pr) on the periphery
of the ligand to be active catalysts for olefin hydroboration. The
catalytic hydroboration of olefins with similar Fe or Co pincer
type complexes is now well explored.20a, 4c, 20b-e However, such
progress is yet to be fully realized in the closely related field of
carbonyl hydroboration.
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 2 of 8
NaHBEt3 has previously been shown to activate inert metal reaction between benzaldehyde and acetophenone (Scheme
1
2
3
4
5
6
7
8
precatalysts to afford systems capable of the hydrosilylation of
alkenes34 and carbonyl compounds.35 The influence of electron-
ics on the catalytic system was investigated by testing deriva-
tives of the acetylacetonate (acac) ligand (i.e., substituting the R
groups on the ligand with electron donating and electron with-
drawing moieties). All activated precatalysts (3b, 3d-3e) exhibit-
ed similar catalytic efficacy except for Fe(dbm)3 (3c) (Scheme
1); side products from coupling of 1a were observed. Unsurpris-
ingly, when FeCl3 was used as the precatalyst, 2a was obtained
in only 10 % yield.
4b).
Scheme 3. Scope of aldehyde hydroboration a
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
The scope of ketone substrates amenable to our hydroboration
protocol was explored (Scheme 2). Progress of the reactions was
conveniently monitored using 11B NMR spectroscopy and GC-
MS sampling of the reaction mixture. In virtually all cases, hy-
droboration of ketones followed by hydrolysis of the boronate
ester afforded the corresponding alcohol in high yield. Examina-
tion of several different ketone substrates demonstrated the gen-
erality of the hydroboration protocol as, in all cases, yields of 2°
alcohols ranged from good to excellent (Scheme 2). Further-
more, introduction of sterically encumbering groups in the sub-
strate did not inhibit product formation as well (compare 2a and
2c).
Scheme 2. Scope of ketone hydroboration a
a
b
Yield after column chromatography. GC-MS shows 100 %
conversion of starting substrate. c Yield after T= 10 hrs.
Scheme 4. Chemoselective Hydroboration Reactions
a
Yield after column chromatography.
The hydroboration of aldehydes at room temperature also afford-
ed quantitative yields of reduced boronate ester products. Unsur-
prisingly, an examination of several different aldehyde substrates
demonstrated the generality of the hydroboration protocol, as in
most cases, yields of 1° alcohols ranged from good to excellent
(Scheme 3). The hydroboration of trans-cinnamaldehyde afford-
ed two products with α,β-unsaturated 3-phenyl-2-propene-1-ol
(5d) as the major product and 2-phenylethanol as the minor
product (5.1:1, Fig. S34). Sterically encumbering groups in the
substrate were also tolerated.
Encouraged by our discovery that hydroboration of both alde-
hydes and ketones could be effected at room temperature, we
chose to examine the potential for chemoselectivity. We sub-
mitted reaction mixtures of both aldehydes and ketones to our
optimized reaction conditions; aliquots from the reaction mix-
1
ture were analyzed using H NMR spectroscopy.36 The reac-
tion between 4-fluorobenzaldehyde and 4-fluoroacetophenone
showed selectivity for hydroboration of the aldehyde. 1H
NMR spectroscopy revealed quantitative consumption of 4-
fluorobenzaldehyde in the reaction mixture after 1 hr (Scheme
4a, Fig. S52). Similar chemoselectivity was observed in the
It also proved possible to delineate the effects of varying sub-
strate electronics employing competition experiments. In the first
competition reaction (aldehydes) selectivity for electron-
2
ACS Paragon Plus Environment

Page 3 of 8
The Journal of Organic Chemistry
withdrawing substituents was observed employing: 4- the ability of cheap and readily available iron salts to catalyze
1
2
fluorobenzaldehyde, benzaldehyde and 4-methoxybenzaldehyde,
hydroboration reactions; typically, such transformations are per-
formed using laboriously prepared homogeneous complexes.
1
based on H NMR spectroscopy (Scheme 4c, Fig. S55). After 1
3
4
5
6
7
8
9
h, addition of a further 1.5 equiv. of HBpin to the reaction mix-
ture afforded complete conversion of 4-fluorobenzaldehyde and
benzaldehyde to reduced products whereas unreacted 4-
methoxybenzaldehyde could still be observed using 1H NMR
spectroscopy. Similarly, the competition reaction for the ketones
Scheme 5. Plausible mechanism for hydroboration of
carbonyl compounds
showed
selectivity
for
electron-poor
substrates;
4-
fluoroacetophenone was favored over acetophenone and 4’-
methylacetophenone (Scheme 4d, Fig. S54). 1H NMR analysis of
the intramolecular hydroboration of 3-acetylbenzaldehyde (6)
showed selectivity for the aldehyde over the ketone. A mixture
of products was observed, 3-acetylbenzyl alcohol (7a) and 1-(3-
(hydroxymethyl)phenyl)ethan-1-ol (7b). The selectivity for the
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
acetyl moiety was not observed as H spectra showed no evi-
dence of the aldehydic proton (Fig. S56).
Baran and co-workers have recently exploited Fe(acac)3 in C-C
bond forming reactions.37,38,39 Elegant mechanistic studies have
suggested that an Fe(acac)3 / PhSiH3 catalyst mixture generates,
in-situ, an “Fe-H” in which the silane acts as stoichiometric re-
ductant.39,40 Holland and co-workers have isolated Fe-H com-
plexes generated by reacting iron chloride complexes with potas-
sium triethylborohydride.41 Interestingly, upon prolonged reac-
tion time the iron hydride complex reacted with BEt3, by-
product, to give an iron dihydridoborate complex. Moreover,
Ritleng and co-workers have isolated and reported the structure
of the active Ni-H that was formed after addition of KHBEt3 to
their Ni catalyst.35 Our attempts to isolate a putative “Fe-H” have
thus far proven unsuccessful. However, our preliminary mecha-
nistic experiments using fourier-transform infrared spectroscopy
(FTIR) suggests the formation of an “Fe-H”. The broad νB-H band
found in NaHBEt3 (1915 cm-1) disappeared upon addition to
Fe(acac)3. Concomitantly, a new peak (1701 cm-1) was observed
which we have tentatively assigned as arising from the νFe-H band
from the in-situ generated “Fe-H” complex (Fig. S57). Further-
more, the intensity of the νFe-H band increased when HBpin was
added to the activated catalyst in solution; the νB-H band of
HBpin (2580 cm-1) completely disappeared (Fig. S58). Typical-
ly, terminal νM-H bands have been reported to lie between 1900 ±
300 cm-1.42 In related experiments, the addition of acetophenone
to the activated pre-catalyst did not show obvious shifts in the
spectra. However, upon addition of HBpin to the mixture of ace-
tophenone / activated pre-catalyst the intensity of the carbonyl
band (νC=O) at 1680 cm-1 decreased significantly due to the im-
mediate onset of catalyzed hydroboration (Fig. S60).
Experimental Section
General Considerations. All reagents were purchased from
commercial vendors, and were used without further purifica-
tion unless otherwise noted. Fe(hfa)3 was prepared according
to the literature.43 All preparations were performed under an
atmosphere of dry argon using schlenk and glove box tech-
niques unless otherwise noted. Solvents (Benzene-d6, Tolu-
ene-d8) were dried over activated molecular sieves (4Å) prior
1
to usage; CDCl3 was used without drying. H, 13C and 11B
NMR spectra were recorded on a Jeol 400 MHz spectrometer
1
at 300K unless otherwise noted. H NMR spectra were refer-
enced to the solvent residual peak (CDCl3, δ 7.26 ppm) and
13C{1H} NMR spectra were referenced to the solvent residual
peak (CDCl3, δ 77.16 ppm). 11B NMR spectra were referenced
1
to BF3 OEt2 (δ 0.00 ppm) as external standard. Data for H
NMR are recorded as follows: the chemical shifts are reported
in (δ, ppm), multiplicity (br = broad, s = singlet, d = doublet, t
= triplet, m = multiplet, dq = doublet of quartet), and coupling
constants in Hz as absolute values. All IR spectra were ob-
tained using a Nicolet iS 5 FT-IR spectrometer equipped with
a specac Di Quest ATR accessory in the glovebox. GC-MS
data were acquired using Thermo Scientific™ ISQ™ Single
Quadrupole system.
General procedure for hydroboration of ketones to 2° al-
cohols (2a-h). A 10 mL oven-dried scintillation vial contain-
ing a stir bar was charged with 10 mol % Fe(acac)3 (35.6 mg,
0.1 mmol), and dissolved in THF (1 mL). 10 mol % NaHBEt3
(100 µL, 0.1 mmol, 1.0 M in THF) was then added, and the
reaction mixture was stirred for ~ 1 minute. Ketone (1.0
mmol), and HBpin (1.5 mmol, 192 mg, 218 µL) were then
added and the reaction mixture was stirred at room tempera-
ture in the glove box for 24 hrs. The reaction mixture was
quenched by addition of diethyl ether (10 mL). Subsequently,
3M NaOH (1 mL) and 30% H2O2 (1 mL) was added and the
reaction mixture was allowed to stir for 1 hr at room tempera-
ture. The organic layer was extracted with diethyl ether (30
mL), and concentrated under reduced pressure. (* Alternative
work up method: Stir the reaction mixture at 50 °C for 1 hr
after addition of 1M HCl (1 mL) and MeOH (3 mL)). After
separation of the ether layer, the aqueous layer was extracted
with diethyl ether (30 mL). The combined organic phases
These results, in concert with the work of Baran and others,23
leads us to propose a hydroboration mechanism in which genera-
tion of an “Fe-H” plays a key role (Scheme 5). The addition of
NaHBEt3 to Fe(acac)3 results in the direct generation of the ac-
tive Fe-H species in which the hydride is transferred from
NaHBEt3. The insertion of the carbonyl substrate to the Fe-H
species forms an iron alkoxide intermediate, which subsequently
acts with HBPin via σ bond metathesis. This leads to the for-
mation of the boronate ester product and regenerates the Fe-H
species closing the catalytic cycle (Scheme 5).
In conclusion, the in-situ activation of an iron precatalyst affords
an operationally convenient method to catalytically hydroborate
aldehydes and ketones. This work represents the first iron-
catalyzed hydroboration of aldehydes and ketones. The simplici-
ty of this methodology adds to the recent trend of utilizing earth
abundant transition metals for applications that were once lim-
ited to precious metals. Most importantly, this work highlights
3
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 4 of 8
were concentrated under reduced pressure. The crude product for 1 hr at room temperature. The organic layer was extracted
1
2
3
4
was purified by flash column chromatography using ethyl
acetate/ hexane (1:5) mixture as eluent to afford the desired
product.
with diethyl ether (30 mL), and concentrated under reduced
pressure. 4.32 mg (5 µL) of mesitylene (internal standard) and
chloroform-d (0.8 mL) was then added to the reaction mix-
ture. The conversion and yield was determined by 1H NMR.
General procedure for hydroboration of aldehydes to 1°
alcohols (5a-j) A 10 mL oven-dried scintillation vial contain-
ing a stir bar was charged with 10 mol % Fe(acac)3 (35.6 mg,
0.1 mmol), and dissolved in THF (1 mL). 10 mol % NaHBEt3
(100 µL, 0.1 mmol, 1.0 M in THF) was then added, and the
reaction mixture was stirred for ~ 1 minute. 1.0 mmol alde-
hyde, and HBpin (1.5 mmol, 192 mg, 218 µL) was then added
and the reaction mixture was stirred at room temperature in
the glove box for 24 hrs. The reaction mixture was quenched
by addition of diethyl ether (10 mL). Subsequently, 3M
NaOH (1 mL) and 30% H2O2 (1 mL) was added and the reac-
tion mixture was allowed to stir for 1 hr at room temperature.
The organic layer was extracted with diethyl ether (30 mL),
and concentrated under reduced pressure. (*Alternative work
up method: Stir the reaction mixture at 50 °C for 1 hr after
addition of 1M HCl (1 mL) and MeOH (3 mL)). After separa-
tion of the ether layer, the aqueous layer was extracted with
diethyl ether (30 mL). The combined organic phases were
concentrated under reduced pressure. The crude product was
purified by flash column chromatography using ethyl acetate/
hexane (1:5) mixture as eluent to afford the desired product.
5
6
7
8
General procedure for competitive chemoselective catalyt-
ic hydroboration of ketones. A 5 mL oven-dried scintillation
vial containing a stir bar was charged with 10 mol %
Fe(acac)3 (3.56 mg, 0.01 mmol), and dissolved in THF (1
mL). 10 mol % NaHBEt3 (10 µL, 0.01 mmol, 1.0 M in THF)
was then added, and the reaction mixture was stirred for ~ 1
minute. A separate 5 mL oven dried scintillation vial was
charged with acetophenone (0.1 mmol, 10.2 µL), 4´-methyl
acetophenone (0.1 mmol, 12.2 µL), 4´-fluoroacetophenone
(0.1 mmol, 10.7 µL), and HBpin (0.15 mmol, 21.8 µL). The
activated precatalyst reaction mixture was then added to the
vial containing the substrates, and the reaction mixture was
stirred at room temperature for 1 hr. An additional 1.5 equiv
of HBpin (21.8 µL) was added after 1 hr, and the reaction
mixture was stirred for 2 hrs. The reaction mixture was
quenched by addition of diethyl ether (10 mL). Subsequently,
3M NaOH (1 mL) and 30% H2O2 (1 mL) was added and the
reaction mixture was allowed to stir for 1 hr at room tempera-
ture. The organic layer was extracted with diethyl ether (30
mL), and concentrated under reduced pressure. 4.32 mg (5
µL) of mesitylene (internal standard) and chloroform-d (0.8
mL) was then added to the reaction mixture. The conversion
and yield was determined by 1H NMR.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
General procedure for chemoselective catalytic hydrobo-
ration. A 5 mL oven-dried scintillation vial containing a stir
bar was charged with 10 mol % Fe(acac)3 (3.56 mg, 0.01
mmol), and dissolved in THF (1 mL). 10 mol % NaHBEt3 (10
µL, 0.01 mmol, 1.0 M in THF) was then added, and the reac-
tion mixture was stirred for ~ 1 minute. A separate 5 mL oven
dried scintillation vial was charged with 0.1 mmol aldehyde,
0.1 mmol ketone, and 0.15 mmol (21.8 µL) HBpin. The acti-
vated precatalyst reaction mixture was then added to the vial
containing the substrates, and the reaction mixture was stirred
at room temperature for 1hr. The reaction mixture was
quenched by addition of diethyl ether (10 mL). Subsequently,
3M NaOH (1 mL) and 30% H2O2 (1 mL) was added and the
reaction mixture was allowed to stir for 1 hr at room tempera-
ture. The organic layer was extracted with diethyl ether (30
mL), and concentrated under reduced pressure. 4.32 mg (5
µL) of mesitylene (Internal standard) and chloroform-d (0.8
mL) was then added to the reaction mixture. The conversion
and yield was determined by 1H NMR.
General procedure for intramolecular hydroboration. A 5
mL oven-dried scintillation vial containing a stir bar was
charged with 10 mol % Fe(acac)3 (3.56 mg, 0.01 mmol), and
dissolved in THF (1 mL). 10 mol % NaHBEt3 (10 µL, 0.01
mmol, 1.0 M in THF) was then added, and the reaction mix-
ture was stirred for ~ 1 minute. A separate 5 mL oven dried
scintillation vial was charged with 4-acetylbenzaldehyde (0.1
mmol,14.81 mg) and HBpin (0.15 mmol, 21.8 µL). The acti-
vated precatalyst reaction mixture was then added to the vial
containing the substrates, and the reaction mixture was stirred
at room temperature for 1 hr. The reaction mixture was
quenched by addition of diethyl ether (10 mL). Subsequently,
3M NaOH (1 mL) and 30% H2O2 (1 mL) was added and the
reaction mixture was allowed to stir for 1 hr at room tempera-
ture. The organic layer was extracted with diethyl ether (30
mL), and concentrated under reduced pressure. 4.32 mg (5
µL) of mesitylene (internal standard) and chloroform-d (0.8
mL) was then added to the reaction mixture. The conversion
and yield was determined by 1H NMR.
General procedure for competitive chemoselective catalyt-
ic hydroboration of aldehydes
A 5 mL oven-dried scintillation vial containing a stir bar was
charged with 10 mol % Fe(acac)3 (3.56 mg, 0.01 mmol), and
dissolved in THF (1 mL). 10 mol % NaHBEt3 (10 µL, 0.01
mmol, 1.0 M in THF) was then added, and the reaction mix-
ture was stirred for ~ 1 minute. A separate 5 mL oven dried
scintillation vial was charged with benzaldehyde (0.1 mmol,
10.2 µL), 4-methoxy benzaldehyde (0.1 mmol, 12.2 µL), 4-
fluorobenzaldehyde (0.1 mmol, 10.7µL), and HBpin (0.15
mmol, 21.8 µL). The activated precatalyst reaction mixture
was then added to the vial containing the substrates, and the
reaction mixture was stirred at room temperature for 1 hr. An
additional 1.5 equiv of HBpin (21.8 µL) was added after 1 hr,
and the reaction mixture was stirred for another hour. The
reaction mixture was quenched by addition of diethyl ether
(10 mL). Subsequently, 3M NaOH (1 mL) and 30% H2O2 (1
mL) was added and the reaction mixture was allowed to stir
Spectral data for 2 alcohols
1-(p-tolyl)ethanol (2a).22c Yield: 114 mg ( 84 %); Colorless
oil. δH (400 MHz; CDCl3): 1.49 (3H, d, J = 4.0 Hz), 1.75 (1H,
d, J = 4.0 Hz), 2.35 (3H, S), 4.85-4.90 (1H, dq, J = 3.6 Hz),
7.17 (2H, d, J = 8.0 Hz), 7.27 (2H, d, J = 8.0 Hz). 13C{1H}
NMR (101 MHz; CDCl3): 143.0, 137.3, 123.0, 125.5, 70.4,
25.2, 21.2. 11B NMR (128 MHz; CDCl3): 23.6. GC-MS (m/z):
136.15.
1-Phenylethanol (2b).29b Yield: 76 mg ( 62 %); Colorless oil.
δH (400 MHz; CDCl3): 1.50 (3H, d, J = 6.4 Hz), 1.80 (1H, Br
S), 4.91 (1H, q, J = 6.4 Hz), 7.28-7.31 (1H, m), 7.34-7.39 (4H,
m). 13C{1H} NMR (101 MHz; CDCl3): 145.9, 128.6, 127.6,
125.5, 70.6, 25.3. 11B NMR (128 MHz; CDCl3): 22.8. GC-MS
(m/z): 122.12.
1-(o-tolyl)ethanol (2c).44 Yield: 113 mg ( 83 %); Colorless oil.
4
ACS Paragon Plus Environment

Page 5 of 8
The Journal of Organic Chemistry
δH (400 MHz; CDCl3): 1.47 (3H, d, J = 4.0 Hz), 1.69 (1H, d, J
7.23-7.27 (1H, m), 7.33 (2H, t, J = 7.6 Hz), 7.39 (2H, d, J =
7.6 Hz). 13C{1H} NMR (101 MHz; CDCl3): 136.8, 131.3,
128.7, 128.6, 127.9, 126.6, 63.9. 11B NMR (128 MHz;
CDCl3): 22.2. GC-MS (m/z): 134.14.
1
2
3
4
5
6
7
8
= 4.0 Hz), 2.35 (3H, S), 5.11-5.17 (1H, dq, J = 3.6 Hz), 7.12-
7.24 (3H, m), 7.52 (1H, d, J = 8.0 Hz). 13C{1H} NMR (101
MHz; CDCl3): 144.0, 134.4, 130.5, 127.3, 126.5, 124.6, 67.0,
24.1, 19.1. 11B NMR (128 MHz; CDCl3): 22.1. GC-MS (m/z):
136.15.
2-methyl-pentan-1-ol (5e). Characterized by GC-MS. See
Figure S73.
1-(4-(trifluoromethyl)phenyl)ethanol (2d).45 Yield: 129 mg (
68 %); Colorless oil. δH (400 MHz; CDCl3): 1.51 (3H, d, J =
8.0 Hz), 1.87 (1H, br S), 4.95-5.00 (1H, dq, J = 3.6 Hz), 7.50
(2H, d, J = 8.0 Hz), 7.61 (wH, d, J = 8.0 Hz). 13C{1H} NMR
(101 MHz; CDCl3): 149.8, 129.8 (q, J =32.42 Hz), 125.8,
125.6 (d, J = 3.84 Hz), 123.0, 70.0, 25.6. 11B NMR (128 MHz;
CDCl3): 22.2. GC-MS (m/z): 190.12.
Cyclohexylmethanol (5f).48 Yield: 80 mg ( 70 %); Colorless
oil. δH (400 MHz; CDCl3): 0.88-0.98 (2H, m), 1.10-1.30 (4H,
m), 1.43-1.52 (1H, m), 1.66-1.76 (5H, m), 3.44(2H, S).
13C{1H} NMR (101 MHz; CDCl3): 68.9, 40.6, 29.7, 26.7,
26.0. 11B NMR (128 MHz; CDCl3): 22.1. GC-MS (m/z):
114.21
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Mesitylmethanol (5g).22c Yield: 127 mg ( 84 %); White pow-
der. δH (400 MHz; CDCl3): 1.56(1H, br S), 2.27 (3H, S), 2.40
(6H, S), 4.72 (2H, d, J = 4.8 Hz), 6.89 (2H, S). 13C{1H} NMR
(101 MHz; CDCl3):137.9, 137.4, 133.9, 129.3, 59.4, 21.1,
19.5. 11B NMR (128 MHz; CDCl3): 21.3. GC-MS (m/z):
151.16.
1-(4-fluorophenyl)ethanol (2e).46 Yield: 88 mg ( 63 %); Color-
less oil. δH (400 MHz; CDCl3): 1.48 (3H, d, J = 4 Hz), 1.78
(1H, br S), 4.87-4.92 (1H, dq, J = 3.6 Hz), 7.03 (2H, t, J = 8.8
Hz), 7.34 (2H, q, J = 5.6 Hz). 13C{1H} NMR (101 MHz;
CDCl3): 162.0 (d, JC-F = 265.5 Hz), 141.6(d, JC-F = 2.89 Hz),
127.2 (d, JC-F = 8.68 Hz), 115.4 (d, JC-F = 21.19 Hz), 69.9,
25.4. 11B NMR (128 MHz; CDCl3): 22.3. GC-MS (m/z):
140.13.
2,2-Diphenylethanol (5h).47 Yield: 131 mg (66 %); White
powder. δH (400 MHz; CDCl3): 1.46 (1H, t, J = 6.0 Hz), 4.16-
4.24 (3H, m), 7.22-7.28 (6H, m), 7.31-7.35 (4H, m), 7.00-7.22
(1H, m). 13C{1H} NMR (101 MHz; CDCl3): 141.4, 128.82,
128.40, 126.9, 66.2, 53.7. 11B NMR (128 MHz; CDCl3): 22.1.
GC-MS (m/z): 198.13.
Diphenylmethanol (2f).22c Yield: 158 mg ( 86 %); White pow-
der. δH (400 MHz; CDCl3): 2.18 (1H, d, J = 4.0 Hz), 5.85 (1H,
d, J = 4.0 Hz), 7.25-7.29 (2H, m), 7.32-7.40 (8H, m). 13C{1H}
NMR (101 MHz; CDCl3): 143.9, 128.7, 127.7, 126.7, 76.4.11B
NMR (128 MHz; CDCl3): 22.3. GC-MS (m/z): 184.13.
1,1-Diphenylpropan-2-ol (2g).47 Yield: 136 mg ( 81 %); White
powder. δH (400 MHz; CDCl3): 1.20 (3H, d, J = 8.0 Hz), 1.64
(1H, d, J = 4.0 Hz), 3.81 (1H, d, J = 8 Hz), 4.52-4.60 (1H, m),
7.17-7.25 (2H, m), 7.28 (4H, d, J = 4.0 Hz), 7.33 (2H, t, J =
8.0 Hz), 7.39 (2H, d, J = 4.0 Hz). 13C{1H} NMR (101 MHz;
CDCl3): 142.6, 141.6, 129.0, 128.8, 128.3, 127.1, 126.7, 70.2,
60.8, 21.5. 11B NMR (128 MHz; CDCl3): 21.7. GC-MS (M-
CH3CO): 168.13.
2-Methoxybenzyl alcohol (5i).49 Yield: 117 mg ( 85 %); Col-
orless oil. δH (400 MHz; CDCl3): 2.30 (1H, br S), 3.87 (3H,
S), 4.69 (2H, d, J = 6.4 Hz), 6.89 (1H, d, J = 8.4 Hz), 6.95
(1H, t, J = 7.4 Hz), 7.26-7.31 (2H, m). 13C{1H} NMR (101
MHz; CDCl3): 157.5, 129.1, 129.1, 128.8, 120.8, 110.3, 62.2,
55.4. 11B NMR (128 MHz; CDCl3): 22.4. GC-MS (m/z):
138.13.
4-Methoxybenzyl alcohol (5j).29b Yield: 115 mg ( 83 %); Col-
orless oil. δH (400 MHz; CDCl3): 1.58 (1H, br S), 3.81 (3H,
S), 4.62 (2H, d, J = 6 Hz), 6.90 (2H, d, J = 8 Hz), 7.30 (2H, d,
J = 8 Hz). 13C{1H} NMR (101 MHz; CDCl3):159.3, 133.2,
128.8, 114.1, 65.2, 55.4. 11B NMR (128 MHz; CDCl3):22.3.
GC-MS (m/z): 138.11.
Dicyclohexylmethanol (2h).45 Yield: 176 mg ( 91 %); White
powder. δH (400 MHz; CDCl3): 0.96 -1.31 (12H, m), 1.39 -
1.48 (2H, m), 1.66 (2H, d, J = 5.8 Hz), 1.74 -1.84 (6H, m),
3.05 (1H, q, J = 5.8 Hz). 13C{1H} NMR (101 MHz; CDCl3):
80.6, 40.0, 30.1, 27.46, 26.69, 26.63, 26.31. 11B NMR (128
MHz; CDCl3): 22.0. GC-MS (m/z): 196.18.
Supporting Information. NMR spectra, and GC-MS data are
included in the SI. The Supporting Information is available
free of charge on the ACS Publications website.
Spectral data for 1 alcohols
Naphthalen-1-ylmethanol (5a).45 Yield: 128 mg ( 81 %); Off
white powder. δH (400 MHz; CDCl3): 1.73 (1H, t, J = 5.6 Hz),
5.17 (2H, d, J = 6.4 Hz), 7.44-7.58 (4H, m), 7.83 (1H, d, J =
8.8), 7.89 (1H, d, J = 8.4), 8.14 (1H, d, J = 8.4). 13C{1H}
NMR (101 MHz; CDCl3):136.4, 134.0, 131.4, 128.8, 128.8,
126.5, 126.0, 125.55, 125.52, 123.8, 63.9. 11B NMR (128
MHz; CDCl3): 22.5. GC-MS (m/z): 158.21.
AUTHOR INFORMATION
Corresponding Author
Corresponding author email: Michael.Findlater@ttu.edu
Funding Sources
No competing financial interests have been declared.
Benzyl alcohol (5b).29b Yield: 86 mg ( 80 %); Colorless oil. δH
(400 MHz; CDCl3): 1.70 (1H, br S), 4.70 (2H, d, J = 6.0 Hz),
7.28 – 7.33 (1H, m), 7.37 (4H, d, J = 4.8 Hz). 13C{1H} NMR
(101 MHz; CDCl3): 141.0, 128.7, 127.77, 127.11, 65.4. 11B
NMR (128 MHz; CDCl3): 22.4. GC-MS (m/z): 108.10.
4-fluorobenzyl alcohol (5c).29b Yield: 112 mg ( 89 %); Color-
less oil. δH (400 MHz; CDCl3): 1.68 (1H, br S), 4.66 (2H, d, J
= 3.6 Hz), 7.04 (2H, t, J = 7.4 Hz), 7.33 (2H, t, J = 5.8 Hz).
13C{1H} NMR (101 MHz; CDCl3): 162.4 (d, JC-F = 246.53
Hz), 136.7, 128.9 (d, JC-F = 8.69 Hz), 115.4 (d, JC-F = 21.19
Hz), 64.8. 11B NMR (128 MHz; CDCl3): 22.6.GC-MS (m/z):
126.11.
ACKNOWLEDGEMENT
The financial support of the Robert A. Welch Foundation (Grant
No. D1807) and the National Science Foundation (Grant CHE-
1554906) is gratefully acknowledged.
REFERENCES
1. (a) Twigg, M. V., Homogeneous Catalysis of Organic Reactions
by Transition Metal Complexes. In Mechanisms of Inorganic and
Organometallic Reactions: Volume 8, Twigg, M. V., Ed. Springer
US: Boston, MA, 1994; pp 363-396; (b) Hegedus, L. S., Transition
metals in the synthesis of complex organic molecules. University
Science Books: 1999; (c) Alper, H., Transition metal organometallics
in organic synthesis. Elsevier: 2012; Vol. 1; (d) Bauer, I.; Knölker,
H.-J., Chem. Rev. 2015, 115, 3170-3387.
3-Phenyl-2-propene-1-ol (5d).48 Yield: 105 mg ( 78 %); Col-
orless oil. δH (400 MHz; CDCl3): 1.46 (1H, br S), 4.34 (2H, t,
J = 5.2 Hz), 6.34-6.41 (1H, m), 6.63 (1H, d, J = 15.6 Hz),
5
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 6 of 8
2. (a) Chakraborty, S.; Guan, H., Dalton Trans. 2010, 39, 7427-
Angew. Chemie. Int. Ed. 2014, 53, 2696-2700; (c) Zhang, L.; Zuo, Z.;
1
2
3
4
5
6
7
8
7436; (b) Miao, J.; Ge, H., Eur. J. Org. Chem. 2015, 2015, 7859-
7868; (c) Su, B.; Cao, Z.-C.; Shi, Z.-J., Acc. Chem. Res. 2015, 48,
886-896.
3. Alberico, D.; Scott, M. E.; Lautens, M., Chem. Rev. 2007, 107,
174-238.
4. (a) Lewis, J. C.; Bergman, R. G.; Ellman, J. A., Acc. Chem. Res.
2008, 41, 1013-1025; (b) Ackermann, L., Chem. Comm. 2010, 46,
4866-4877; (c) Greenhalgh, M. D.; Thomas, S. P., Chem. Commun.
2013, 49, 11230-11232.
5. Ritleng, V.; Sirlin, C.; Pfeffer, M., Chem. Rev. 2002, 102, 1731-
1770.
6. (a) Roy, A. K., A Review of Recent Progress in Catalyzed
Homogeneous Hydrosilation (Hydrosilylation). In Adv. Organomet.
Chem. , Robert West, A. F. H.; Mark, J. F., Eds. Academic Press:
2007; Vol. Volume 55, pp 1-59; (b) Marciniec, B., Hydrosilylation: a
comprehensive review on recent advances. Springer Science &
Business Media: 2008; Vol. 1.
7. (a) Mkhalid, I. A. I.; Barnard, J. H.; Marder, T. B.; Murphy, J.
M.; Hartwig, J. F., Chem. Rev. 2010, 110, 890-931; (b) Hartwig, J. F.,
Accounts of Chemical Research 2012, 45, 864-873.
Wan, X.; Huang, Z., J. Am. Chem. Soc. 2014, 136, 15501-15504.
20. (a) Wu, J. Y.; Moreau, B.; Ritter, T., J. Am. Chem. Soc. 2009,
131, 12915-12917; (b) Chen, J.; Xi, T.; Lu, Z., Org. Lett. 2014, 16,
6452-6455; (c) Chen, J.; Xi, T.; Ren, X.; Cheng, B.; Guo, J.; Lu, Z.,
Org. Chem. Front. 2014, 1, 1306-1309; (d) Zheng, J.; Sortais, J.-B.;
Darcel, C., ChemCatChem 2014, 6, 763-766; (e) Tseng, K.-N. T.;
Kampf, J. W.; Szymczak, N. K., ACS Catal. 2015, 5, 411-415.
21. (a) Cho, B. T., Chem. Soc. Rev. 2009, 38, 443-452; (b) Magano,
J.; Dunetz, J. R., Org. Process. Res. Dev. 2012, 16, 1156-1184.
22. (a) Koren-Selfridge, L.; Londino, H. N.; Vellucci, J. K.;
Simmons, B. J.; Casey, C. P.; Clark, T. B., Organometallics 2009, 28,
2085-2090; (b) Chong, C. C.; Hirao, H.; Kinjo, R., Angew. Chemie.
Int. Ed. 2015, 54, 190-194; (c) Kaithal, A.; Chatterjee, B.;
Gunanathan, C., Org. Lett. 2015, 17, 4790-4793.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
23. Bagherzadeh, S.; Mankad, N. P., Chem. Commun. 2016, 52,
3844-3846.
24. Zhang, G.; Zeng, H.; Wu, J.; Yin, Z.; Zheng, S.; Fettinger, J. C.,
Angew. Chemie. Int. Ed. 2016, 128, 14581-14584.
25. (a) Lindsley, C. W.; DiMare, M., Tetrahedron Lett. 1994, 35,
5141-5144; (b) Giffels, G.; Dreisbach, C.; Kragl, U.; Weigerding, M.;
Waldmann, H.; Wandrey, C., Angew. Chemie. Int. Ed. 1995, 34,
2005-2006; (c) Almqvist, F.; Torstensson, L.; Gudmundsson, A.;
Frejd, T., Angew. Chemie. Int. Ed. 1997, 36, 376-377; (d) Sarvary, I.;
Almqvist, F.; Frejd, T., Chem. Eur. J. 2001, 7, 2158-2166; (e)
Oluyadi, A. A.; Ma, S.; Muhoro, C. N., Organometallics 2013, 32,
70-78.
26. (a) Bandini, M.; Cozzi, P. G.; de Angelis, M.; Umani-Ronchi *,
A., Tetrahedron Lett. 2000, 41, 1601-1605; (b) Roh, S.-G.; Park, Y.-
C.; Park, D.-K.; Kim, T.-J.; Jeong, J. H., Polyhedron 2001, 20, 1961-
1965; (c) Locatelli, M.; Cozzi, P. G., Angew. Chemie. Int. Ed. 2003,
42, 4928-4930; (d) Fleury, L. M.; Ashfeld, B. L., Org. Lett. 2009, 11,
5670-5673; (e) Lummis, P. A.; Momeni, M. R.; Lui, M. W.;
McDonald, R.; Ferguson, M. J.; Miskolzie, M.; Brown, A.; Rivard,
E., Angew. Chemie. Int. Ed. 2014, 53, 9347-9351.
8. (a) Collet, F.; Dodd, R. H.; Dauban, P., Chem. Comm. 2009,
5061-5074; (b) Collet, F.; Lescot, C.; Dauban, P., Chem. Soc. Rev.
2011, 40, 1926-1936.
9. Ishihara, Y.; Baran, P. S., Synlett 2010, 2010, 1733-1745.
10. (a) Ackermann, L., J. Org. Chem. 2014, 79, 8948-8954; (b)
Chirik, P. J., Acc. Chem. Res. 2015, 48, 1687-1695; (c) Li, Y.-Y.; Yu,
S.-L.; Shen, W.-Y.; Gao, J.-X., Acc. Chem. Res. 2015, 48, 2587-2598.
11. (a) Matteson, D. S., Chem. Rev. 1989, 89, 1535-1551; (b)
Burgess, K.; Ohlmeyer, M. J., Chem. Rev. 1991, 91, 1179-1191; (c)
Miyaura, N.; Suzuki, A., Chem. Rev. 1995, 95, 2457-2483; (d)
Pereira, S.; Srebnik, M., J. Am. Chem. Soc. 1996, 118, 909-910; (e)
Beletskaya, I.; Pelter, A., Tetrahedron 1997, 53, 4957-5026; (f)
Suzuki, A., J. Organomet. Chem. 1999, 576, 147-168; (g) Carroll, A.-
M.; O'Sullivan, T. P.; Guiry, P. J., Adv. Synth. Catal. 2005, 347, 609-
631; (h) Lennox, A. J. J.; Lloyd-Jones, G. C., Chem. Soc. Rev. 2014,
43, 412-443.
12. (a) Burgess, K.; Van der Donk, W. A.; Westcott, S. A.; Marder,
T. B.; Baker, R. T.; Calabrese, J. C., J. Am. Chem. Soc. 1992, 114,
9350-9359; (b) Evans, D. A.; Fu, G. C.; Hoveyda, A. H., J. Am.
Chem. Soc. 1992, 114, 6671-6679; (c) Ramachandran, P. V.;
Jennings, M. P.; Brown, H. C., Org. Lett. 1999, 1, 1399-1402; (d)
Colin, S.; Vaysse-Ludot, L.; Lecouve, J.-P.; Maddaluno, J., J. Chem.
Soc. Perkin Trans. 1 2000, 4505-4511; (e) Vogels, C. M.; O'Connor,
P. E.; Phillips, T. E.; Watson, K. J.; Shaver, M. P.; Hayes, P. G.;
Westcott, S. A., Can. J. Chem. 2001, 79, 1898-1905; (f) Crudden,
Cathleen M.; Edwards, D., Eur. J. Org. Chem. 2003, 2003, 4695-
4712; (g) Rubina, M.; Rubin, M.; Gevorgyan, V., J. Am. Chem. Soc.
2003, 125, 7198-7199; (h) Crudden, C. M.; Hleba, Y. B.; Chen, A. C.,
J. Am. Chem. Soc. 2004, 126, 9200-9201; (i) Edwards, D. R.; Hleba,
Y. B.; Lata, C. J.; Calhoun, L. A.; Crudden, C. M., Angew. Chemie.
Int. Ed. 2007, 46, 7799-7802.
13. (a) Burgess, K.; Jaspars, M., Organometallics 1993, 12, 4197-
4200; (b) Caballero, A.; Sabo-Etienne, S., Organometallics 2007, 26,
1191-1195.
14. Yamamoto, Y.; Fujikawa, R.; Umemoto, T.; Miyaura, N.,
Tetrahedron 2004, 60, 10695-10700.
15. (a) Miyaura, N., Hydroboration, Diboration, Silylboration, and
Stannylboration. In Catalytic Heterofunctionalization, Wiley-VCH
Verlag GmbH: 2001; pp 1-45; (b) Brown, J. M., Rhodium-Catalyzed
Hydroborations and Related Reactions. In Modern Rhodium-
Catalyzed Organic Reactions, Wiley-VCH Verlag GmbH & Co.
KGaA: 2005; pp 33-53.
16. Obligacion, J. V.; Chirik, P. J., Org. Lett. 2013, 15, 2680-2683.
17. (a) Obligacion, J. V.; Chirik, P. J., J. Am. Chem. Soc. 2013, 135,
19107-19110; (b) Palmer, W. N.; Diao, T.; Pappas, I.; Chirik, P. J.,
ACS Catal. 2015, 5, 622-626.
27. Yadav, S.; Pahar, S.; Sen, S. S., Chem. Commun. 2017, 53,
4562-4564.
28. (a) Arrowsmith, M.; Hadlington, T. J.; Hill, M. S.; Kociok-
Kohn, G., Chem. Commun. 2012, 48, 4567-4569; (b) Fohlmeister, L.;
Stasch, A., Chem. Eur. J. 2016, 22, 10235-10246; (c) Manna, K.; Ji,
P.; Greene, F. X.; Lin, W., J. Am. Chem. Soc. 2016, 138, 7488-7491;
(d) Mukherjee, D.; Osseili, H.; Spaniol, T. P.; Okuda, J., J. Am.
Chem. Soc. 2016, 138, 10790-10793; (e) Mukherjee, D.; Shirase, S.;
Spaniol, T. P.; Mashima, K.; Okuda, J., Chem. Commun. 2016, 52,
13155-13158; (f) Osseili, H.; Mukherjee, D.; Beckerle, K.; Spaniol,
T. P.; Okuda, J., Organometallics 2017, 36, 3029-3034.
29. (a) Yang, Z.; Zhong, M.; Ma, X.; De, S.; Anusha, C.;
Parameswaran, P.; Roesky, H. W., Angew. Chemie. Int. Ed. 2015, 54,
10225-10229; (b) Jakhar, V. K.; Barman, M. K.; Nembenna, S., Org.
Lett. 2016, 18, 4710-4713.
30. Hadlington, T. J.; Hermann, M.; Frenking, G.; Jones, C., J. Am.
Chem. Soc. 2014, 136, 3028-3031.
31. Blake, A. J.; Cunningham, A.; Ford, A.; Teat, S. J.; Woodward,
S., Chem. Eur. J. 2000, 6, 3586-3594.
32. Wu, Y.; Shan, C.; Sun, Y.; Chen, P.; Ying, J.; Zhu, J.; Liu, L.;
Zhao, Y., Chem. Commun. 2016, 52, 13799-13802.
33. Chen, S.; Yan, D.; Xue, M.; Hong, Y.; Yao, Y.; Shen, Q., Org.
Lett. 2017, 19, 3382-3385.
34. (a) Kamata, K.; Suzuki, A.; Nakai, Y.; Nakazawa, H.,
Organometallics 2012, 31, 3825-3828; (b) Chen, J.; Cheng, B.; Cao,
M.; Lu, Z., Angew. Chemie. Int. Ed. 2015, 54, 4661-4664; (c)
Nikonov, G. I., ChemCatChem 2015, 7, 1918-1919; (d) Du, X.;
Zhang, Y.; Peng, D.; Huang, Z., Angew. Chemie. Int. Ed. 2016, 55,
6671-6675.
35. Bheeter, L. P.; Henrion, M.; Brelot, L.; Darcel, C.; Chetcuti, M.
J.; Sortais, J.-B.; Ritleng, V., Adv. Synth. Catal. 2012, 354, 2619-
2624.
36. (a) Tondreau, A. M.; Lobkovsky, E.; Chirik, P. J., Org. Lett.
2008, 10, 2789-2792; (b) Smith, A. D.; Saini, A.; Singer, L. M.;
Phadke, N.; Findlater, M., Polyhedron 2016, 114, 286-291.
37. Lo, J. C.; Gui, J.; Yabe, Y.; Pan, C.-M.; Baran, P. S., Nature
2014, 516, 343-348.
18. (a) Zhang, L.; Peng, D.; Leng, X.; Huang, Z., Angew. Chemie.
Int. Ed. 2013, 52, 3676-3680; (b) Zhang, L.; Peng, D.; Leng, X.;
Huang, Z., Angew. Chemie. 2013, 125, 3764-3768.
19. (a) Zhang, L.; Zuo, Z.; Leng, X.; Huang, Z., Angew. Chemie.
2014, 126, 2734-2738; (b) Zhang, L.; Zuo, Z.; Leng, X.; Huang, Z.,
6
ACS Paragon Plus Environment

Page 7 of 8
The Journal of Organic Chemistry
38. Dao, H. T.; Li, C.; Michaudel, Q.; Maxwell, B. D.; Baran, P. S.,
45. Wekesa, F. S.; Arias-Ugarte, R.; Kong, L.; Sumner, Z.;
1
2
3
4
J. Am. Chem. Soc. 2015, 137, 8046-8049.
39. Lo, J. C.; Yabe, Y.; Baran, P. S., J. Am. Chem. Soc. 2014, 136,
1304-1307.
40. Koji, K.; Teruaki, M., Chem. Lett. 1992, 21, 1137-1140.
41. Yu, Y.; Brennessel, W. W.; Holland, P. L., Organometallics
2007, 26, 3217-3226.
McGovern, G. P.; Findlater, M., Organometallics 2015, 34, 5051-
5056.
46. Li, J.; Wang, C.; Xue, D.; Wei, Y.; Xiao, J., Green Chem. 2013,
15, 2685-2689.
47. Hu, X.; Zhang, G.; Bu, F.; Lei, A., ACS Catal. 2017, 7, 1432-
1437.
5
6
7
8
9
42. Kaesz, H. D.; Saillant, R. B., Chem. Rev. 1972, 72, 231-281.
43. Chambers, K.; Cherniak, E.; Taylor, G.; Yu, J., Can. J. Chem.
1976, 54, 2116-2123.
44. Zuo, Z.; Zhang, L.; Leng, X.; Huang, Z., Chem. Commun. 2015,
51, 5073-5076.
48. Shaikh, N. S.; Junge, K.; Beller, M., Org. Lett. 2007, 9, 5429-
5432.
49. Zhang, G.; Scott, B. L.; Hanson, S. K., Angew. Chemie. Int. Ed.
2012, 51, 12102-12106.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
7
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 8 of 8
TOC Graphic:
1
2
3
4
O
O
B
• commercially available catalyst
• operationally convenient
• room temperature catalysis
• 18 examples, up to 91 % yield
O
O
O
Fe
Catalysis
B
H
+
O
R
R1
R
R1
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
8
ACS Paragon Plus Environment