Nickel-Catalysed Allylboration of Aldehydes

Article abstract of DOI:10.1055/s-0039-1690091

A nickel catalyst for the allylboration of aldehydes is reported, facilitating the preparation of homoallylic alcohols in high diastereoselectivity. The observed diastereoselectivities and NMR experiments suggest that allylation occurs through a well-defined six-membered transition state, with nickel acting as a Lewis acid.

Full text of DOI:10.1055/s-0039-1690091

SYNTHESIS
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© Georg Thieme Verlag Stuttgart · New York
2020, 52, A–L
paper
A
en
F. M. Dennis et al.
Paper
Synthesis
Nickel-Catalysed Allylboration of Aldehydes
Francesca M. Dennis
Craig C. Robertson
O
OH
R
H
Benjamin M. Partridge*
0
0
0
0-0
0
0
2-
8
5
5
0-9
9
9
4
Ph
B(pin)
R
[Ni] cat.
Department of Chemistry, University of Sheffield, Dainton
Building, Sheffield, S3 7HF, UK
b.m.partridge@sheffield.ac.uk
KF, THF, RT
Ph
up to >19:1 d.r.
59–95% yield
• 26 examples
• Allylation through a cyclic transition state
• Ni acts as a Lewis acid catalyst
Received: 13.01.2020
Accepted after revision: 04.03.2020
Published online: 18.03.2020
ucts.14 Our results also complement reports of Ni-catalysed
reductive allylations of carbonyls15 and Ni-catalysed allyla-
tions via double bond transposition of alkenyl borates.16
DOI: 10.1055/s-0039-1690091; Art ID: ss-2020-z0028-op
Abstract A nickel catalyst for the allylboration of aldehydes is report-
ed, facilitating the preparation of homoallylic alcohols in high diastereo-
selectivity. The observed diastereoselectivities and NMR experiments
suggest that allylation occurs through a well-defined six-membered
transition state, with nickel acting as a Lewis acid.
• Privileged alkylboron reagent
O
• Utilised in reactions catalysed by
Pd, Rh, Ir, Cu and Co catalysts
B
O
This study:
O
R3
OH
R3
Key words allylboration, boronic esters, catalysis, homoallylic alco-
hols, nickel
R1
B(pin)
R4
R
H
R
Ni(OAc)2, dppf
KF, THF, RT
R2 R1
R2
R4
Scheme 1 Allylboronic ester and its use with transition metal catalysts
The use of arylboron reagents in combination with tran-
sition-metal catalysis enables a wide range of C–C and C–
heteroatom bond-forming reactions.1 However, reactions
involving the corresponding alkylboronic esters2 are under-
developed despite the recent growth in methods to prepare
these valuable reagents.3 Allylboron reagents are a privi-
leged exception, with catalysts based on metals such as pal-
ladium,4 rhodium,5 iridium,6 copper,7 and cobalt8 reported
to promote their reactions, including cross-couplings and
allylborations. In comparison, Ni-catalysed transformations
of allylboron reagents are rare.9,10 The ability to develop
nickel catalysts which promote the functionalisation of alk-
ylboron reagents is desirable. This is due to the higher
abundance and lower cost of nickel compared with many
precious metals, in addition to the opportunities to exploit
its diverse reactivity in the development of new transfor-
mations.11
We started by investigating the effect of adding Ni(OAc)2
and a variety of ligands on the yield of the allylboration of
aldehyde 1a with boronic ester 2 (Table 1).17 In the absence
of Ni, there was a modest background reaction after 18
hours, with a 41% yield of homoallylic alcohol 3a being ob-
tained (entry 1). The addition of Ni(OAc)2 provided little
improvement. However, a combination of Ni(OAc)2 and
dppf in a 2.2:1 ratio led to an increased yield (entry 2). Ad-
dition of KF as a base was beneficial (entry 3), though
Cs2CO3 led to a reduced yield (entry 4). From a survey of li-
gands, addition of dppf led to the most active catalyst. Oth-
er ligand classes including diamines and P,N-ligands led to
moderate yields at best (entries 5–9). Using dppf, the load-
ing of the catalyst could be reduced. Although a 76% yield of
3a was obtained within 5 hours using 37 mol% of Ni(OAc)2
and 15 mol% of dppf, similar yields were obtained with 12
mol% of Ni(OAc)2 and 5.5 mol% of dppf after 24 hours. In the
interests of reducing the overall cost of the reagents, we
chose the lower Ni loading to explore the scope of the reac-
tion. These conditions could be scaled up, with an 84% yield
of alcohol 3a being isolated as a single diastereomer (entry
10).
As part of a programme aimed at the development of
metal-catalysed transformations of alkylboronic esters,12
we report herein a procedure for Ni-catalysed allylboration
(Scheme 1).10,13 Previously, isolated allylnickel species have
been shown to be nucleophilic, and stoichiometric reac-
tions with aldehydes give homoallylic alcohols as prod-
© 2020. Thieme. All rights reserved. Synthesis 2020, 52, A–L
Georg Thieme Verlag KG, Rüdigerstraße 14, 70469 Stuttgart, Germany

B
F. M. Dennis et al.
Paper
Synthesis
Table 1 Evaluation of the Effect of the Reaction Conditions on the
Table 2 Allylboration of Primary and Secondary Boronic Estersa
Yield of the Allylborationa
4-ClC6H4CHO (1 equiv)
R1
B(pin)
OH
R3
Ph
B(pin)
O
OH
Ni(OAc)2·4H2O (12 mol%)
dppf (5.5 mol%)
R2
R3
2
(1.2 equiv)
R2 R1
5a–h
4a–h
KF (1.2 equiv)
H
(1.2 equiv)
Cl
Ni(OAc)2·4H2O (45 mol%)
ligand (20 mol%)
base (1.2 equiv)
THF, RT, 18 h
Ph
Cl
Cl
1a
3a
Boronic Ester
Product
Yieldb
65%
d.r.c
THF, RT, 18 h
d.r. >19:1b
OH
Entry
Ligand
Base
Yieldc
Me
B(pin)
Ar
4:1
1d
2
–
–
41%
70%
84%
45%
78%
82%
68%
54%
52%
84%
H
4a
Me
E/Z = 4:1
dppf
dppf
dppf
–
( )-5a
3
KF
OH
4
Cs2CO3
H
B(pin)
Ar
99%
>19:1
5
XantPhos
dppbz
L1
KF
KF
KF
KF
KF
KF
Me
Me
4b
6
( )-5b
7
OH
Ar
Cl
8
L2
89%
95%
79%
>19:1
n/a
9
PyPhos
dppf
Ar
10e
4c
(pin)B
( )-5c
OH Me
Me
PPh2
PPh2
PPh2
B(pin)
Fe
Ar
O
4d
( )-5d
PPh2
PPh2
XantPhos
PPh2
OH
dppf
L1
dppbz
Me
Ph Ph
H
N
Ar
n/a
Me
B(pin)
Me Me
N
4e
H
H2N
NH2
N
PPh2
( )-5e
L2
PyPhos
OH
H
a Reactions were run on 0.044 mmol scale unless otherwise stated.
B(pin)
b The d.r. was determined by 1H NMR analysis of the crude reaction mix-
Ar
69%
>9:1
ture.
c Yield determined by 1H NMR analysis using 1,3,5-trimethoxybenzene as
( )-4f
( )-5f
an internal standard.
d Without Ni(OAc)2·4H2O.
e 12 mol% of Ni(OAc)2 and 5.5 mol% of dppf; 0.33 mmol scale; isolated
yield.
OH
Ar
B(pin)
75%
1:3 (E/Z)
9:1 (E/Z)
Me
Me
(
(
)-4g
Next, we explored the scope with respect to the allylbo-
ronic ester reagent (Table 2). Both E- and Z-crotyl boronic
esters reacted to give the anti and syn homoallylic alcohols
5a and 5b, respectively. This is consistent with allylboration
occurring through a well-defined cyclic transition state. In
both cases, the E/Z ratio of the allylboron matched the d.r. of
the product. This suggests that isomerisation of the allyl
nucleophile does not occur on the timescale of the reaction.
Further boronic esters tested included aryl chloride 4c and
2-substituted boronic ester 4d, both of which reacted
smoothly. The reaction of trisubstituted allyl boronic ester
4e demonstrated that formation of a quaternary centre is
possible and that 1,3-allylic transposition does not occur
prior to allylation.
( )-5g
OH
B(pin)
76%d
Ph
Ar
Ph
)-4h
( )-5h
a Reactions were run on 0.33 mmol scale unless otherwise stated.
Ar = 4-Cl-C6H4
b Isolated yield.
c The d.r. was determined by 1H NMR analysis of the crude reaction mixture.
d Reaction run on a 0.29 mmol scale.
The method was also successful with secondary allyl-
boronic esters 4f–h (Table 2). Cyclic boronic ester 4f reacted
to give syn-homoallylic alcohol 5f in high yield as a single
diastereomer. Acyclic boronic ester 4g reacted to give
alkene 5g in a modest 3:1 Z/E ratio, consistent with previ-
ous allylborations using secondary pinacol allylboronic es-
ters.18 Instead, 4h reacted to give the corresponding E-
alkene 5h in good stereochemical control. Usually, a steri-
© 2020. Thieme. All rights reserved. Synthesis 2020, 52, A–L

C
F. M. Dennis et al.
Paper
Synthesis
cally unhindered allylboron reagent is needed to obtain E-
selectivity for the homoallylic alcohol product.19 However,
it has been observed previously that aryl-substituted sec-
ondary allyl boronic esters react to give E-homoallylic alco-
hols preferentially.20 The E-selectivity could be accounted
for by Ni acting as a Lewis acid catalyst, as a moderate
switch from Z- to E-selectivity has also been observed using
Lewis acid catalysts.21
We next explored the scope of the aldehydes tolerated
in the Ni-catalysed allylboration. Boronic ester 2 reacted
with a range of benzaldehyde derivatives to give anti-ho-
moallylic alcohols 3a–r in good to excellent yield (Scheme
2). The relative configuration of 3f was confirmed by X-ray
crystallography.22 The remainder of the products were as-
signed through comparison with literature data or by anal-
ogy to 3f. Functional groups tolerated include aryl halides,
nitrile, nitro and trifluoromethyl. Substitution at the ortho
position did not lower the reaction efficiency. Heteroaro-
matic pyridyl-, furyl- and thiophenyl-derived aldehydes
also reacted in good yield. The reaction conditions were
also successful with aliphatic aldehydes 1q and 1r.
The reaction of (S)-1s provided homoallylic alcohol
(S,S,R)-3s, the syn,anti-diastereomer, which was isolated as
a single diastereomer (Scheme 3). The absolute configura-
tion was confirmed by X-ray crystallography.22 The diaste-
reoselectivity observed (>6:1) is greater than for the corre-
sponding reaction of aldehyde 1s with boronic ester 4a as
described by Roush and co-workers, which gave a 1:1 mix-
ture of syn,anti and anti,anti products.23 The syn diastereo-
selectivity is consistent with a chelate-controlled anti-Cram
addition to aldehyde (S)-1s.24
Ph
B(pin)
OH
O
2 (1.2 equiv)
H
Ni(OAc)2·4H2O (12 mol%)
dppf (5.5 mol%)
O
O
O
Ph
O
KF (1.2 equiv)
THF, RT, 18 h
(S)-1s
3s
42%
d.r. >6:1
Scheme 3 Nickel-catalysed allylboration of aldehyde (S)-1s
The Ni-catalysed allylboration reaction could also be
carried out on gram scale without a decrease in reaction ef-
ficiency (Scheme 4).
Ph
B(pin)
O
OH
2 (1.2 equiv)
R
H
O
R
Ni(OAc)2·4H2O (12 mol%)
dppf (5.5 mol%)
Ph
B(pin)
O
OH
Ph
3a–r
d.r. >19:1
2 (1.2 equiv)
KF (1.2 equiv)
THF, RT, 18 h
1a–r
H
Ni(OAc)2⋅4H2O (12 mol%)
dppf (5.5 mol%)
Ph
O
KF (1.2 equiv)
THF, RT, 18 h
3a 84%
Cl
Cl
X = Cl
3b 83%
3c 80%
3d 70%
3e 85%
3f 89%
3g 95%
= OMe
= Me
= H
= Br
= CN
= CF3
1a
(1 g scale)
3a
H
90%
d.r. >19:1
H
3h 84%
3i 78%
X = OMe
= CN
X
Scheme 4 Nickel-catalysed allylboration on gram scale
X
O
O
H
O
O
H
H
H
To give insight to the role of the Ni catalyst, we per-
formed a series of 11B NMR experiments (Figure 1). First we
analysed a solution containing Ni(OAc)2, dppf, KF and bo-
ronic ester 2 in THF. A characteristic peak for the boronic
ester was observed at 33 ppm. This signal remained un-
changed over a period of 3 hours. Next, 1 equivalent of
benzaldehyde was added to the solution and the mixture
was reanalysed. Within 30 minutes, a new peak was ob-
served by boron NMR at 22 ppm, which is consistent with a
borate, presumably structure 6 formed through allylbora-
tion. This suggests that the Ni catalyst is unlikely to undergo
transmetalation with the boronic ester, as an AcO-B(pin)
by-product was not observed before addition of the alde-
hyde. Instead, the data are more consistent with Ni acting
as a Lewis acid catalyst.
N
O
X
X = Me 3j 71%
= F
3n
69%
3o
62%
3k 82%
3m
= NO2 3l 79%
85%
O
O
Br
O
H
H
Ph
H
S
3p
80%
3q
69%
3r
59%
Scheme 2 Scope of Ni-catalysed allylboration with respect to the car-
bonyl electrophile. Reactions were performed on 0.33 mmol scale.
Diastereomeric ratios were determined by 1H NMR analysis of the crude
reaction mixture. Isolated yields are reported
© 2020. Thieme. All rights reserved. Synthesis 2020, 52, A–L

D
F. M. Dennis et al.
Paper
Synthesis
were collected at 100 K on a Bruker D8 Venture diffractometer
equipped with a Photon 100 CMOS detector using a CuK microfocus
X-ray source. Crystals were mounted in fomblin oil on a MiTiGen mi-
croloop and cooled in a stream of cold N2.
2-(2E)-3-Phenyl-2-propen-1-yl-4,4,5,5-tetramethyl-1,3,2-dioxa-
borolane (2)
Using a modification of the procedure by Singaram and co-workers,25
a flask containing magnesium turnings (0.583 g, 24.0 mmol) was
purged with nitrogen and charged with anhydrous THF (30 mL) fol-
lowed by HB(pin) (3.0 mL, 20 mmol). Cinnamyl chloride (2.8 mL, 20
mmol) was added dropwise over 5 min at room temperature. The
mixture was stirred for 1 h and another portion of cinnamyl chloride
(1.4 mL, 10.0 mmol) was added. After 5 h of stirring at room tempera-
ture, the magnesium turnings were fully consumed. The reaction was
diluted with hexanes (20 mL) and quenched with aqueous HCl (0.1 M,
60 mL). Caution! Hydrogen evolution. The mixture was extracted
with hexanes (2 × 20 mL) and the combined organic layers were dried
(MgSO4), filtered and concentrated in vacuo. The residue was purified
by flash chromatography (2% Et2O/petroleum ether) to give boronic
ester 2 (1.29 g, 26%) as a colourless solid. The analytical data are con-
sistent with the literature.26
Figure 1 Overlaid 11B NMR spectra for (a) boronic ester 2, (b) boronic
ester 2 in the presence of the Ni catalyst, (c) boronic ester 2 in the pres-
ence of the Ni catalyst with aldehyde 1a added after 3 hours
In summary, we have developed a Ni-catalysed allyl-
boration of aldehydes with allylboronic esters. The high dia-
stereoselectivities obtained are consistent with allylation
occurring through a cyclic transition state. An NMR study
suggests that the role of the Ni-catalyst is likely to be as a
Lewis acid.
Rf = 0.06 (2% Et2O/petroleum ether).
1H NMR (400 MHz, CDCl3):  = 7.29–7.17 (m, 4 H, ArH), 7.12–7.09 (t,
J = 7.2 Hz, 1 H, ArH), 6.30 (d, J = 15.8 Hz, 1 H, PhCH=C), 6.20 (dt,
J = 15.8, 7.2 Hz, 1 H, PhCH=CH), 1.86 (d, J = 7.2 Hz, 2 H, CH2), 1.24 (s,
12 H, 4 × CH3).
13C NMR (101 MHz, CDCl3):  = 138.2 (C), 130.2 (CH), 128.4 (2 × CH),
126.5 (CH), 126.3 (CH), 125.8 (2 × CH), 83.4 (2 × OC), 24.8 (4 × CH3).
11B NMR (128 MHz, CDCl3):  = 32.9.
All reagents and solvents used were supplied by commercial sources
without further purification unless specified. All air-sensitive reac-
tions were carried out under a nitrogen atmosphere using oven-dried
apparatus. Anhydrous Et2O and THF were dried and purified by pas-
sage through activated alumina columns using a solvent purification
system. The petroleum ether used was in the 40–60 °C boiling range.
Thin-layer chromatography (TLC) was performed on aluminium-
backed plates pre-coated with silica. Compounds were visualised by
exposure to UV light or by dipping the plates into solutions of vanillin
followed by heating. All flash chromatography was carried out using
silica gel (mesh 40–63). Melting points were measured using a
Linkam HFs91 heating stage, used in conjunction with a TC92 control-
ler and are uncorrected. Specific rotations were measured using a po-
larimeter. Infrared spectra were recorded on a Perkin Elmer 100 FT
instrument using neat compounds. NMR spectra were recorded on
Bruker Avance 400 and 500 instruments at the indicated frequency
(101, 128, 126, 377 and 400 MHz) as dilute solutions in deuterated
chloroform (CDCl3) as the solvent at ambient temperature. All chemi-
cal shifts () are reported in parts per million (ppm) relative to residu-
al protio solvent (H: CHCl3 = 7.27 ppm) or the solvent itself (C:
CDCl3 = 77.0 ppm). All multiplicities are designated by the following
abbreviations: s = singlet, br s = broad singlet, d = doublet,
dd = doublet of doublets, dt = doublet of triplets, td = triplet of dou-
blets, ddd = doublet of doublets of doublets, q = quartet, br q = broad
quartet, m = multiplet. All coupling constants (J) are reported in Hertz
(Hz). 13C NMR spectra were acquired by DEPT-Q experiments as stan-
dard. Standard 13C NMR experiments were acquired when quaternary
carbons were hard to distinguish by DEPT-Q. Signals for carbon atoms
directly attached to boron were not observed. 19F NMR spectra were
acquired as decoupled spectra. High-resolution mass spectra were re-
corded using either electrospray ionisation (ESI) or electron ionisa-
tion (EI) by the Mass Spectrometry Service at the Department of
Chemistry, University of Sheffield. Single-crystal X-ray intensity data
2-(2E)-2-Buten-1-yl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4a)
Using a modification of the procedure by Morken and co-workers,27
a
flask containing Pd2(dba)3 (66.3 mg, 0.075 mmol) and bis(pinacola-
to)diboron (3.80 g, 15.0 mmol) was purged with nitrogen and charged
with anhydrous THF (7 mL) followed by crotyl bromide (1.50 mL, 15.0
mmol). The mixture was stirred at 60 °C for 18 h. The mixture was
cooled to room temperature, concentrated in vacuo and purified by
flash chromatography (2% Et2O/pentane), to give the boronic ester 4a
(905 mg, 34%, E/Z = 4:1) as a colourless oil. The data are consistent
with the literature.26
Rf = 0.07 (2% Et2O/petroleum ether).
1H NMR (400 MHz, CDCl3):  = 5.57–5.40 (m, 2 H, HC=CH), 1.67–1.65
(m, 3 H, CHCH3), 1.62–1.60 (m, 2 H, CH2), 1.24 (s, 12 H, 4 × CCH3).
13C NMR (101 MHz, CDCl3):  = 125.9 (CH), 125.3 (CH), 83.1 (2 × OC),
24.8 (4 × CH3), 18.1 (CH3). Characteristic signals for the Z isomer:
125.0 (CH), 123.8 (CH), 14.3 (CH3).
11B NMR (128 MHz, CDCl3):  = 32.7.
4,4,5,5-Tetramethyl-2-[(2E)-3-(4-chlorophenyl)prop-2-en-1-yl]-
1,3,2-dioxaborolane (4c)
Using a modification of the procedure by Morken and co-workers,4i
an oven-dried flask containing 4-chlorobenzaldehyde (1a) (2.00 g,
14.0 mmol) was purged under nitrogen. THF (70 mL) was added and
the mixture was cooled to –78 °C. Vinylmagnesium bromide (25 mL,
0.7 M in THF, 17.0 mmol) was added and the mixture was warmed to
room temperature and stirred for 3 h. Saturated aqueous ammonium
chloride (40 mL) was added and the mixture was extracted with Et2O
(3 × 30 mL). The combined organic layers were dried (MgSO4), filtered
© 2020. Thieme. All rights reserved. Synthesis 2020, 52, A–L

E
F. M. Dennis et al.
Paper
Synthesis
and concentrated in vacuo to give 1-(4-chlorophenyl)prop-2-en-1-ol
(2.40 g) as an orange oil. The material was used without further puri-
fication.
4,4,5,5-Tetramethyl-2-(3-methylbut-2-en-1-yl)-1,3,2-dioxaboro-
lane (4e)
Using a modification of the procedure by Morken and co-workers,27
a
flask containing Pd2(dba)3 (0.024 g, 0.027 mmol) and B2Pin2 (0.768 g,
5.3 mmol) was purged with nitrogen and charged with anhydrous
THF (5 mL). 1-Bromo-3-methylbut-2-ene (0.9 mL, 5.3 mmol) was
added. The mixture was stirred at 60 °C for 18 h. The mixture was
concentrated in vacuo and purified by flash chromatography (2% EtO-
Ac/petroleum ether) to give the boronic ester 4e (699 mg, 88%) as a
pale yellow oil. The data are consistent with the literature.30
1H NMR (400 MHz, CDCl3):  = 5.23 (ddd, J = 7.6, 4.7, 1.5 Hz, 1 H, CH),
1.70 (s, 3 H, CH3), 1.60 (m, 5 H, CH3 and CH2), 1.25 (m, 12 H, 4 × CCH3).
13C NMR (101 MHz, CDCl3):  = 131.5 (C), 118.5 (CH), 83.1 (2 × C), 25.7
An oven-dried round-bottom flask containing 1-(4-chlorophe-
nyl)prop-2-en-1-ol (1.00 g, 6.00 mmol) was purged under nitrogen.
CH2Cl2 (10 mL) was added and the mixture was cooled to 0 °C. SOCl2
(1.29 mL, 17.9 mmol) was added and the mixture was stirred at 0 °C
for 3 h and then at room temperature for 2 h. The mixture was
quenched with ice water (30 mL) and extracted with CH2Cl2 (3 × 10
mL). The combined organic layers were dried (MgSO4), filtered and
concentrated in vacuo to give 1-chloro-4-[(1E)-3-chloroprop-1-en-1-
yl]benzene (1.11 g) as a brown solid. The material was used without
further purification.
Using a modification of the procedure by Singaram and co-workers,25
a round-bottom flask containing magnesium turnings (127 mg, 5.29
mmol) was purged with nitrogen. Anhydrous THF (15 mL) was added
followed by HB(pin) (0.60 mL, 4.4 mmol). 1-Chloro-4-[(1E)-3-chloro-
prop-1-en-1-yl]benzene (0.83 g, 4.4 mmol) was added dropwise over
5 min at room temperature. The mixture was stirred for 1 h and addi-
tional 1-chloro-4-[(1E)-3-chloroprop-1-en-1-yl]benzene (0.41 g, 2.2
mmol, 0.5 equiv) was added. After stirring at room temperature over-
night the magnesium turnings were fully consumed. The mixture was
diluted with hexanes (10 mL) and quenched with aqueous HCl (0.1 M,
30 mL). Caution! Hydrogen evolution. The mixture was extracted
with hexanes (3 × 10 mL) and the combined organic layers were dried
(MgSO4), filtered and concentrated in vacuo. The crude material was
purified by flash chromatography (2% Et2O/petroleum ether) to give
boronic ester 4c (94.4 mg, 5%) as a pale yellow oil. The data are consis-
tent with the literature.28
(CH3), 24.8 (4 × CH3), 17.6 (CH3).
11B NMR (128 MHz, CDCl3):  = 32.8.
(±)-2-(Cyclohex-2-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaboro-
lane (4f)
Using a modification of the procedure by Marder and co-workers,31
a
solution of CuCl2 (8.0 mg, 0.060 mmol), IMes (20.0 mg, 0.060 mmol)
and KOMe (252 mg, 3.60 mmol) in THF (12 mL) was stirred for 10
min. B2Pin2 (1.83 g, 7.2 mmol) and KOMe (252 mg, 3.60 mmol) were
added and the mixture was stirred for 10 min. 3-Bromocyclohexene
(0.69 mL, 6.0 mmol) was added and the mixture was stirred over-
night. The mixture was diluted with Et2O (20 mL), filtered through a
plug of Celite and concentrated in vacuo. The residue was purified by
flash chromatography (5% Et2O/petroleum ether) to give the boronic
ester 4f (844 mg, 68%) as a colourless oil. The data are consistent with
the literature.31
Rf = 0.23 (2% Et2O/petroleum ether).
Rf = 0.50 (5% Et2O/petroleum ether).
1H NMR (400 MHz, CDCl3):  = 7.27–7.20 (m, 4 H, ArH), 6.29–6.26 (m,
2 H, HC=CH), 1.86 (d, J = 6.5 Hz, 2 H, CH2), 1.23 (s, 12 H, 4 × CH3).
13C NMR (101 MHz, CDCl3):  = 136.6 (C), 132.0 (C), 129.1 (CH), 128.5
(2 × CH), 127.1 (2 × CH), 127.0 (CH), 83.5 (2 × C), 24.8 (4 × CH3).
11B NMR (128 MHz, CDCl3):  = 32.7.
1H NMR (400 MHz, CDCl3):  = 5.86–5.56 (m, 2 H, HC=CH), 2.11–1.94
(m, 2 H, CH2), 1.87–1.72 (m, 2 H, CH2), 1.71–1.54 (m, 3 H, CH2CH), 1.24
(s, 12 H, 4 × CH3).
13C NMR (101 MHz, CDCl3):  = 127.6 (CH), 126.1 (CH), 83.1 (2 × C),
25.0 (CH2), 24.8 (2 × CH3), 24.7 (2 × CH3), 24.1 (CH2), 22.5 (CH2).
11B NMR (128 MHz, CDCl3):  = 33.4.
4,4,5,5-Tetramethyl-2-(2-methylprop-2-en-1-yl)-1,3,2-dioxaboro-
lane (4d)
(±)-4,4,5,5-Tetramethyl-2-(1-methyl-2-propen-1-yl)-1,3,2-dioxa-
borolane (4g)
Using a modification of the procedure by Singaram and co-workers,25
a flask containing magnesium turnings (0.583 g, 24.0 mmol) was
purged with nitrogen and charged with anhydrous THF (30 mL) fol-
lowed by HB(pin) (3.0 mL, 20 mmol). 3-Chloro-2-methyl-1-propene
(2.0 mL, 20 mmol) was added dropwise over 5 min at room tempera-
ture. The mixture was stirred for 1 h and another portion of 3-chloro-
2-methyl-1-propene (2.0 mL, 20.0 mmol) was added. After 18 h of
stirring at room temperature the magnesium turnings were fully con-
sumed. The reaction was diluted with hexanes (20 mL) and quenched
with aqueous HCl (0.1 M, 60 mL). Caution! Hydrogen evolution. The
mixture was extracted with hexanes (3 × 20 mL) and the combined
organic layers were dried (MgSO4), filtered and concentrated in vac-
uo. The residue was purified by flash column chromatography (2%
Et2O/petroleum ether) to give boronic ester 4d (1.02 g, 27%) as a co-
lourless oil. The data are consistent with the literature.29
Using a modification of the procedure by Singaram and co-workers,25
a flask containing magnesium turnings (0.516 g, 21.2 mmol) was
purged with nitrogen and charged with anhydrous THF (30 mL) fol-
lowed by HB(pin) (2.5 mL, 17.7 mmol). Crotyl bromide (1.5 mL, 17.7
mmol) was added dropwise over 5 min at room temperature. The
mixture was stirred for 1 h and another portion of crotyl bromide (1.5
mL, 17.7 mmol) was added. After 5 h of stirring at room temperature
the magnesium turnings were fully consumed. The reaction was di-
luted with hexanes (20 mL) and quenched with aqueous HCl (0.1 M,
60 mL). Caution! Hydrogen evolution. The mixture was extracted
with hexanes (2 × 20 mL) and the combined organic layers were dried
(MgSO4), filtered and concentrated in vacuo. The residue was purified
by flash chromatography (2% Et2O/petroleum ether) to give boronic
ester 4g (1.60 g, 59%) as a colourless oil. The data are consistent with
the literature.25
Rf = 0.40 (2% Et2O/n-hexane).
1H NMR (400 MHz, CDCl3):  = 4.66 (d, J = 7.2 Hz, 2 H, C=CH2), 1.76 (s,
3 H, CH2=CCH3), 1.71 (s, 2 H, BCH2), 1.24 (s, 12 H, 4 × CH3).
13C NMR (101 MHz, CDCl3):  = 142.9 (C), 110.2 (CH2), 83.2 (2 × C),
24.7 (4 × CH3), 24.5 (CH3).
11B NMR (128 MHz, CDCl3):  = 32.7.
Rf = 0.20 (2% Et2O/petroleum ether).
1H NMR (400 MHz, CDCl3):  = 5.93 (ddd, J = 17.3, 10.3, 7.1 Hz, 1 H,
CH=CH2), 4.96 (dt, J = 17.3, 1.7 Hz, 1 H, CH=CHAHB), 4.91 (dt, J = 10.3,
1.7 Hz, 1 H, CH=CHAHB), 1.97–1.81 (m, 1 H, CH), 1.23 (s, 12 H,
4 × CCH3), 1.08 (d, J = 5.8 Hz, 3 H, CHCH3).
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F. M. Dennis et al.
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Synthesis
13C NMR (101 MHz, CDCl3):  = 140.8 (1 × CH), 111.9 (CH2), 83.1
(2 × C), 24.6 (4 × CH3), 14.0 (CH3).
11B NMR (128 MHz, CDCl3):  = 33.2.
13C NMR (101 MHz, CDCl3):  = 140.3 (C), 140.1 (C), 137.5 (CH), 133.0
(C), 128.4 (2 × CH), 128.2 (2 × CH), 128.0 (4 × CH), 126.7 (CH), 118.7
(CH2), 76.5 (CH), 59.3 (CH).
(±)-anti-1-(4-Chlorophenyl)-2-phenylbut-3-en-1-ol (3a); Gram-
Scale Procedure
(±)-2-(1-Phenyl-2-propen-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxa-
borolane (4h)
An oven-dried flask was charged with 4-chlorobenzaldehyde (1.01 g,
7.21 mmol), Ni(OAc)2·4H2O (0.219 g, 0.880 mmol), KF (0.535 g, 9.21
mmol) and dppf (0.198 mg, 0.357 mmol) and purged under nitrogen
for 1 h. Boronic ester 2 (2.09 g, 8.55 mmol) and THF (12 mL) were
added and the mixture stirred at room temperature for 18 h. H2O (20
mL) was added and the mixture was extracted with Et2O (3 × 20 mL).
The combined organic layers were dried (MgSO4), filtered and evapo-
rated in vacuo. The crude material was purified by flash chromatogra-
phy (10% Et2O/n-hexane) to give alcohol 3a (1.67 g, 90%) as a pale yel-
low oil. The data are consistent with the literature.34 See above for
NMR data.
Using a modification of the procedure by Aggarwal and co-workers,32
a Schlenk flask containing benzyl N,N-diisopropylcarbamate12 (1.16 g,
4.97 mmol) was backfilled with nitrogen three times. TMEDA (0.74
mL, 4.97 mmol) and anhydrous Et2O (12 mL, 0.2 M) were added and
the mixture was cooled to –78 °C. s-BuLi (3.80 mL, 1.3 M in hexanes,
4.67 mmol) was added dropwise and the mixture was stirred at –78 °C
for 4 h. 2-Vinyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.5 mL,
2.9 mmol) was added dropwise and the mixture was stirred at –78 °C
for 1 h. A solution of MgBr2 in Et2O [2.50 mL, 8.77 mmol; freshly
prepared from Mg turnings (0.210 g, 8.75 mmol), Et2O (3 mL) and 1,2-
dibromoethane (0.75 mL, 8.75 mmol)] was added dropwise and the
mixture was stirred at 34 °C for 18 h. The mixture was cooled to room
temperature and NH4Cl (20 mL) and Et2O (15 mL) were added. The
mixture was then extracted with Et2O (3 × 15 mL) and the combined
organic layers were dried (MgSO4), filtered and concentrated in vac-
uo. The residue was purified by flash chromatography (2% Et2O/petro-
leum ether) to give the boronic ester 4h (451 mg, 64%) as a colourless
oil. There is only partial data available in the literature.33
(±)-anti-1-(4-Chlorophenyl)-2-methylbut-3-en-1-ol (5a)
The title compound was prepared according to general procedure 1
from 4-chlorobenzaldehyde (48.3 mg, 0.344 mmol) and boronic ester
4a (72.8 g, 0.400 mmol). The crude material was purified by flash
chromatography (10% Et2O/pentane) to give alcohol 5a (44.2 mg, 65%)
as a pale yellow oil. The data are consistent with the literature.35
Rf = 0.20 (2% Et2O/petroleum ether).
Rf = 0.19 (10% Et2O/n-hexane).
1H NMR (400 MHz, CDCl3):  = 7.31–7.11 (m, 5 H, ArH), 6.10 (ddd,
J = 17.1, 10.2, 8.2 Hz, 1 H, CH=CH2), 5.02–5.00 (m, 2 H, CH2), 3.23 (d,
J = 8.2 Hz, 1 H, ArCH), 1.21 (s, 12 H, 4 × CH3).
13C NMR (101 MHz, CDCl3):  = 141.1 (C), 138.7 (CH), 128.4 (4 × CH),
125.5 (CH), 114.5 (CH2), 83.6 (2 × C), 24.6 (4 × CH3).
11B NMR (128 MHz, CDCl3):  = 32.2.
HRMS (EI): m/z [M]+ calcd for C15H21BO2: 244.1634; found: 244.1629.
1H NMR (400 MHz, CDCl3):  (anti isomer) = 7.35–7.23 (m, 4 H, ArH),
5.82–5.68 (m, 1 H, C=CH), 5.23–5.22 (m, 2 H, CH=CH2), 4.36 (d, J = 7.8
Hz, 1 H, HOCH), 2.45–2.41 (m, 1 H, C=CCH), 2.16 (s, 1 H, OH), 0.88 (d,
J = 6.8 Hz, 3 H, CH3). Characteristic signals from the minor diastereo-
isomer were observed at:  = 5.11–4.99 (m, 1 H, CH=CH2), 4.62 (d,
J = 5.4 Hz, 1 H, HOCH), 2.59–2.52 (m, 1 H, C=CCH), 1.93 (s, 1 H, OH),
1.00 (d, J = 6.8 Hz, 1 H, CH3).
13C NMR (126 MHz, CDCl3):  = 140.8 (C), 140.2 (CH), 133.3 (C), 128.4
(2 × CH), 128.2 (2 × CH), 117.3 (CH2), 76.5 (CH), 46.4 (CH), 16.4 (CH3).
Characteristic signals from the minor diastereoisomer were observed
at:  = 140.9 (C), 139.8 (CH), 133.0 (C), 127.8 (2 × CH), 116.0 (CH2),
77.1 (CH), 44.6 (CH), 13.8 (CH3).
Preparative Scale Nickel-Catalysed Allylboration; General Proce-
dure 1
An oven-dried flask was charged with an aldehyde (0.330 mmol),
Ni(OAc)2·4H2O (10.0 mg, 0.040 mmol), KF (21.0 mg, 0.390 mmol) and
dppf (9.5 mg, 0.017 mmol) and purged under nitrogen for 1 h. The bo-
ronic ester (0.390 mmol, 1.2 equiv) and THF (3 mL) were added and
the mixture stirred at room temperature for 18 h. H2O (10 mL) was
added and the mixture was extracted with Et2O (3 × 10 mL). The com-
bined organic layers were dried (MgSO4), filtered and evaporated in
vacuo. The crude material was purified by flash chromatography.
(±)-syn-1-(4-Chlorophenyl)-2-methylbut-3-en-1-ol (5b)
The title compound was prepared according to general procedure 1
from 4-chlorobenzaldehyde (42.3 mg, 0.301 mmol) and boronic ester
4b (73.6 mg, 0.404 mmol). The crude material was purified by flash
chromatography (10% Et2O/n-hexane) to give alcohol 5b (59.0 mg,
99%) as a colourless oil. The data are consistent with the literature.35
Rf = 0.16 (10% Et2O/n-hexane).
(±)-anti-1-(4-Chlorophenyl)-2-phenylbut-3-en-1-ol (3a)
1H NMR (400 MHz, CDCl3):  = 7.35–7.29 (m, 2 H, ArH), 7.27–7.24 (m,
2 H, ArH), 5.75 (ddd, J = 17.3, 10.6, 7.0 Hz, 1 H, C=CH), 5.13–5.02 (m, 2
H, CH=CH2), 4.62 (d, J = 5.4 Hz, 1 H, HOCH), 2.56 (qd, J = 6.8, 5.4 Hz, 1
H, C=CCH), 1.92, (s, 1 H, OH), 1.00 (d, J = 6.8 Hz, 3 H, CH3).
13C NMR (126 MHz, CDCl3):  = 141.0 (C), 139.9 (CH), 133.0 (C), 128.2
(2 × CH), 127.9 (2 × CH), 116.0 (CH2), 76.5 (CH), 44.6 (CH), 13.8 (CH3).
The title compound was prepared according to general procedure 1
from 4-chlorobenzaldehyde (45.3 mg, 0.332 mmol) and boronic ester
2 (99.3 mg, 0.407 mmol). The crude material was purified by flash
chromatography (10% Et2O/petroleum ether) to give alcohol 3a (70.4
mg, 84%) as a colourless oil. The data are consistent with the litera-
ture.34
Rf = 0.18 (10% Et2O/petroleum ether).
(±)-anti-1,2-Bis(4-chlorophenyl)but-3-en-1-ol (5c)
1H NMR (400 MHz, CDCl3):  = 7.25–7.15 (m, 5 H, ArH), 7.07–7.03 (m,
4 H, ArH), 6.24 (ddd, J = 17.1, 10.2, 9.6 Hz, 1 H, CH=CH2), 5.28 (dd,
J = 10.2, 1.2 Hz, 1 H, CH=CHAHB), 5.24 (dd, J = 17.1, 1.2 Hz, 1 H,
CH=CHAHB), 4.81 (d, J = 7.9 Hz, 1 H, HOCH), 3.48 (dd, J = 9.6, 7.9 Hz, 1
H, C=CCH), 2.39 (d, J = 2.2 Hz, 1 H, OH).
The title compound was prepared according to general procedure 1
from 4-chlorobenzaldehyde (47.1 mg, 0.335 mmol) and boronic ester
4c (111 mg, 0.379 mmol). The crude material was purified by flash
chromatography (10% Et2O/n-hexane) to give alcohol 5c (87.4 mg,
89%) as a colourless oil.
Rf = 0.09 (10% Et2O/n-hexane).
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F. M. Dennis et al.
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Synthesis
IR (ATR): 3418 (O–H), 2904, 1596, 1490, 1090, 1013, 923, 820 cm–1
.
13C NMR (101 MHz, CDCl3):  = 141.2 (C), 133.0 (C), 130.9 (CH), 128.3
(2 × CH), 127.8 (2 × CH), 127.6 (CH), 76.6 (CH), 43.0 (CH), 25.2 (CH2),
23.5 (CH2), 21.0 (CH2).
1H NMR (400 MHz, CDCl3):  = 7.22–7.16 (m, 4 H, ArH), 7.06 (dd,
J = 8.7, 2.1 Hz, 2 H, ArH), 7.00–6.90 (m, 2 H, ArH), 6.18 (ddd, J = 17.1,
10.1, 8.9 Hz, 1 H, CH=CH2), 5.31 (dd, J = 10.1, 0.8 Hz, 1 H, CH=CHAHB),
5.24 (dd, J = 17.1, 0.8 Hz, 1 H, CH=CHAHB), 4.76 (dd, J = 7.9, 2.2 Hz, 1 H,
HOCH), 3.48 (dd, J = 8.9, 7.9 Hz, 1 H, C=CCH), 2.32 (d, J = 2.2 Hz, 1 H,
OH).
13C NMR (101 MHz, CDCl3):  = 140.0 (C), 138.7 (C), 137.1 (CH), 133.3
(C), 132.6 (C), 129.6 (2 × CH), 128.6 (2 × CH), 128.2 (2 × CH), 128.0
(2 × CH), 119.1 (CH2), 76.5 (CH), 58.6 (CH).
(±)-(Z)-1-(4-Chlorophenyl)-pent-3-en-1-ol (5g)
The title compound was prepared according to general procedure 1
from 4-chlorobenzaldehyde (45.2 mg, 0.321 mmol) and boronic ester
4g (72.5 mg, 0.398 mmol). The crude material was purified by flash
chromatography (10% Et2O/n-hexane) to give alcohol 5g (47.3 mg,
75%) as a colourless oil.
HRMS (ESI): m/z [M + Na]+ calcd for C16H14O35Cl2Na: 315.0319; found:
315.0322.
The literature data for the E-5g and Z-5g isomers has inconsistencies.
Based on reference 18b we have assigned the major isomer as Z-5g.
Rf = 0.23 (10% Et2O/n-hexane).
1H NMR (400 MHz, CDCl3):  = 7.36–7.29 (m, 4 H, ArH), 5.70–5.66 (m,
1 H, C=CH), 5.45–5.38 (m, 1 H, C=CH), 4.74–4.71 (m, 1 H, HOCH),
2.64–2.34 (m, 2 H, CH2), 1.96 (br s, 1 H, OH), 1.62 (d, J = 7.4 Hz, 3 H,
CH3). Characteristic signals from (E)-5g were observed at:  = 4.68–
4.66 (m, 1 H, HOCH), 1.71 (d, J = 6.4 Hz, 3 H, CH3).
13C NMR (101 MHz, CDCl3):  (E isomer) = 142.5 (C), 133.1 (C), 128.5
(2 × CH), 128.1 (CH), 127.2 (2 × CH), 125.2 (CH), 73.1 (CH), 37.0 (CH2),
13.0 (CH3). Characteristic signals from (E)-5g were observed at:
 = 133.0 (C), 130.0 (C), 127.8 (2 × CH), 127.2 (2 × CH), 126.3 (CH),
72.7 (CH), 42.8 (CH2), 18.1 (CH3).
(±)-1-(4-Chlorophenyl)-3-methylbut-3-en-1-ol (5d)
The title compound was prepared according to general procedure 1
from 4-chlorobenzaldehyde (46.7 mg, 0.332 mmol) and boronic ester
4d (77.6 mg, 0.426 mmol). The crude material was purified by flash
column chromatography on silica gel (10% Et2O/n-hexane) to give al-
cohol 5d (61.8 mg, 95%) as a pale yellow oil. The data are consistent
with the literature.34
Rf = 0.16 (10% Et2O/n-hexane).
1H NMR (400 MHz, CDCl3):  = 7.33 (s, 4 H, ArH), 4.95 (d, J = 1.4 Hz, 1
H, C=CHAHB), 4.87 (d, J = 1.4 Hz, 1 H, C=CHAHB), 4.80 (ddd, J = 7.8, 5.6,
2.2 Hz, 1 H, HOCH), 2.48–2.33 (m, 2 H, CHCH2), 2.16 (d, J = 2.2 Hz, 1 H,
OH), 1.81 (s, 3 H, CH3).
Data from Reference 18b
13C NMR (101 MHz, CDCl3):  = 142.5 (C), 142.0 (C), 133.1 (C), 128.5
Z-isomer
1H NMR (400 MHz, CDCl3):  = 7.29–7.32 (m, 4 H, ArH), 5.69–5.62 (m,
1 H, CH=CH), 5.36–5.43 (m, 1 H, CH=CH), 4.70 (br t, J = 6.4 Hz, 1 H,
ArCH), 2.58–2.50 (m, 1 H, CHACHB), 2.47–2.40 (m, 1 H, CHACHB), 2.02
(br s, 1 H, OH), 1.59 (dt, J = 6.8, 0.8 Hz, 3 H, CH3).
13C NMR (100 MHz, CDCl3):  = 142.5 (C), 133.1 (C), 128.4 (CH), 128.1
(CH), 127.2 (CH), 125.1 (CH), 73.1 (CH), 37.0 (CH2), 13.0 (CH3).
(2 × CH), 127.1 (2 × CH), 114.5 (CH2), 70.7 (CH), 48.4 (CH2), 22.3 (CH3).
(±)-1-(4-Chlorophenyl)-2,2-dimethylbut-3-en-1-ol (5e)
The title compound was prepared according to general procedure 1
from 4-chlorobenzaldehyde (47.8 mg, 0.340 mmol) and boronic ester
4e (81.4 mg, 0.415 mmol). The crude material was purified by flash
chromatography (10% Et2O/n-hexane) to give alcohol 5e (56.7 mg,
79%) as a colourless oil. The data are consistent with the literature.36
Data from Reference 38
Rf = 0.2 (10% Et2O/n-hexane).
E-isomer
1H NMR (400 MHz, CDCl3):  = 7.32–7.25 (m, 4 H, ArH), 5.91 (dd,
J = 17.5, 10.8 Hz, 1 H, CH=CH2), 5.19 (dd, J = 10.8, 1.1 Hz, 1 H,
CH=CHACHB), 5.11 (dd, J = 17.5, 1.1 Hz, 1 H, CH=CHACHB), 4.44 (s, 1 H,
CHOH), 2.06 (d, J = 2.1 Hz, 1 H, OH), 1.02 (s, 3 H, CH3), 0.97 (s, 3 H,
CH3).
13C NMR (101 MHz, CDCl3):  = 144.7 (CH), 139.1 (C), 133.1 (C), 129.1
(2 × CH), 127.6 (2 × CH), 114.4 (CH2), 79.9 (CH), 42.3 (C), 24.4 (CH3),
20.7 (CH3).
1H NMR (400 MHz, CDCl3):  = 7.33–7.27 (m, 4 H), 5.70–5.56 (m, 1 H),
5.43–5.36 (m, 1 H), 4.72–4.68 (m, 1 H), 2.58–2.31 (m, 2 H), 2.05 (s, 1
H), 1.60 (d, J = 6.0 Hz, 3 H).
13C NMR (100 MHz, CDCl3):  = 142.57, 133.11, 128.49, 128.49,128.05,
127.24, 127.24, 125.21, 73.14, 36.95, 12.96.
Z-isomer
1H NMR (400 MHz, CDCl3):  = 4.67–4.64 (m, 1 H), 2.10 (s, 1 H), 1.69
(d, J = 6.0 Hz, 3 H).
13C NMR (100 MHz, CDCl3):  = 142.53, 133.02, 129.91, 128.47,128.47,
127.20, 127.20, 126.31, 72.74, 42.81, 18.02.
(±)-syn-(4-Chlorophenyl)(cyclohex-2-en-1-yl)methanol (5f)
The title compound was prepared according to general procedure 1
from 4-chlorobenzaldehyde (49.9 mg, 0.355 mmol) and boronic ester
4f (85.3 mg, 0.409 mmol). The crude material was purified by flash
chromatography (10% Et2O/n-hexane) to give alcohol 5f (54.9 mg,
69%) as a colourless oil. The data are consistent with the literature.37
(±)-(E)-1-(4-Chlorophenyl)-4-phenylbut-3-en-1-ol (5h)
The title compound was prepared using a modification of general
procedure 1 from 4-chlorobenzaldehyde (40.8 mg, 0.290 mmol), bo-
ronic ester 4h (82.9 mg, 0.340 mmol), Ni(OAc)2·4H2O (8.9 mg, 0.036
mmol), KF (19.6 mg, 0.338 mmol), dppf (7.9 mg, 0.014 mmol) and
THF (3 mL). The crude material was purified by flash chromatography
(10% Et2O/n-hexane) to give alcohol 5h (57.2 mg, 76%) as a white sol-
id. The data are consistent with the literature.39
Rf = 0.16 (10% Et2O/n-hexane).
1H NMR (400 MHz, CDCl3):  = 7.32–7.26 (m, 4 H, ArH), 5.83 (ddd,
J = 10.0, 6.1, 3.5 Hz, 1 H, CHCH=CH), 5.37 (dd, J = 10.0, 1.9 Hz, 1 H,
CHCH=CH), 4.57 (d, J = 6.2 Hz, 1 H, HOCH), 2.54–2.45 (m, 1 H,
CH=CHCH), 2.20–1.93 (m, 2 H, CH=CHCH2), 1.92 (s, 1 H, OH), 1.75
(ddd, J = 14.7, 9.2, 4.8 Hz, 1 H, CHCHAHB), 1.61 (ddd, J = 17.0, 9.4, 5.5
Hz, 1 H, CHCH2CHAHB), 1.54–1.45 (m, 2 H, CHCH2CHAHB, CHCHAHB).
Rf = 0.30 (10% Et2O/n-hexane); mp 123–125 °C (petroleum ether). No
literature data available.
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F. M. Dennis et al.
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1H NMR (400 MHz, CDCl3):  = 7.38–7.21 (m, 9 H, ArH), 6.51 (d,
J = 15.9 Hz, 1 H, CH=CHPh), 6.27–6.12 (m, 1 H, CH=CHPh), 4.81 (ddd,
J = 8.1, 5.2, 3.2 Hz, 1 H, HOCH), 2.73–2.58 (m, 2 H, CH2), 2.08 (d, J = 3.2
Hz, 1 H, OH). Characteristic signals from (Z)-5h were observed at:
 = 6.60 (d, J = 12.4 Hz, 1 H, CH=CHAr), 5.79–5.65 (m, 1 H, CH=CHPh),
2.88–2.80 (m, 2 H, CH2), 1.97 (d, J = 3.5 Hz, 1 H, OH).
13C NMR (101 MHz, CDCl3):  (E isomer) = 142.3 (C), 137.0 (C), 133.9
(CH), 133.2 (C), 128.6 (2 × CH), 128.6 (2 × CH), 127.5 (CH), 127.2
(2 × CH), 126.2 (2 × CH), 125.3 (CH), 73.0 (CH), 43.1 (CH2). Character-
istic signals from (Z)-5h were observed at: 132.1 (C), 128.7 (2 × CH),
128.2 (2 × CH), 127.3 (2 × CH), 126.9 (CH), 73.5 (CH), 38.2 (CH2).
13C NMR (101 MHz, CDCl3):  = 141.8 (C), 140.6 (C), 137.8 (CH), 128.3
(2 × CH), 128.3 (2 × CH), 127.9 (2 × CH), 127.4 (CH), 126.7 (2 × CH),
126.6 (CH), 118.4 (CH2), 77.2 (CH), 59.2 (CH).
(±)-anti-1-(4-Bromophenyl)-2-phenylbut-3-en-1-ol (3e)
The title compound was prepared according to general procedure 1
from 4-bromobenzaldehyde (62.9 mg, 0.344 mmol) and boronic ester
2 (99.4 mg, 0.407 mmol). The crude material was purified by flash
chromatography (10% Et2O/n-hexane) to give alcohol 3e (88.3 mg,
85%) as a pale yellow oil. The data are consistent with the literature.41
Rf = 0.16 (10% Et2O/n-hexane).
1H NMR (400 MHz, CDCl3):  = 7.36–7.30 (m, 2 H, ArH), 7.24–7.16 (m,
3 H, ArH), 7.05–7.00 (m, 4 H, ArH), 6.23 (ddd, J = 17.0, 10.1, 9.1 Hz, 1
H, CH=CH2), 5.32–5.24 (m, 2 H, CH=CH2), 4.80 (dd, J = 8.3, 2.3 Hz, 1 H,
HOCH), 3.48 (dd, J = 9.1, 8.3 Hz, 1 H, C=CCH), 2.36 (d, J = 2.3 Hz, 1 H,
OH).
13C NMR (101 MHz, CDCl3):  = 140.7 (C), 140.1 (C), 137.5 (CH), 131.0
(2 × CH), 128.5 (2 × CH), 128.4 (2 × CH), 128.2 (2 × CH), 126.8 (CH),
121.2 (C), 118.8 (CH2), 76.6 (CH), 59.3 (CH).
(±)-anti-1-(4-Methoxyphenyl)-2-phenylbut-3-en-1-ol (3b)
The title compound was prepared according to general procedure 1
from p-anisaldehyde (45.5 mg, 0.334 mmol) and boronic ester 2 (97.5
mg, 0.399 mmol). The crude material was purified by flash chroma-
tography (10% Et2O/petroleum ether) to give alcohol 3b (70.4 mg,
83%) as a colourless oil. The data are consistent with the literature.40
Rf = 0.04 (10% Et2O/petroleum ether).
1H NMR (400 MHz, CDCl3):  = 7.24–7.19 (m, 2 H, ArH), 7.17–7.13 (m,
1 H, ArH), 7.10–7.05 (m, 4 H, ArH), 6.77–6.69 (m, 2 H, ArH), 6.27 (ddd,
J = 17.0, 10.2, 9.0 Hz, 1 H, CH=CH2), 5.30–5.23 (m, 2 H, CH=CH2), 4.81
(d, J = 7.9 Hz, 1 H, HOCH), 3.76 (s, 3 H, CH3), 3.55 (dd, J = 9.0, 7.9 Hz, 1
H, C=CCH), 2.32 (s, 1 H, OH).
13C NMR (100 MHz, CDCl3):  = 158.8 (C), 140.7 (C), 138.2 (CH), 134.0
(C), 128.3 (4 × CH), 127.8 (2 × CH), 126.5 (CH), 118.2 (CH2), 113.3
(2 × CH), 76.8 (CH), 59.3 (CH), 55.1 (CH3).
(±)-anti-1-(4-Cyanophenyl)-2-phenylbut-3-en-1-ol (3f)
The title compound was prepared according to general procedure 1
from 4-cyanobenzaldehyde (42.7 mg, 0.326 mmol) and boronic ester
2 (96.1 mg, 0.394 mmol). The crude material was purified by flash
chromatography (10% Et2O/petroleum ether) to give alcohol 3f (72.0
mg, 89%) as a white solid. The data are consistent with the litera-
ture.42
Rf = 0.05 (10% Et2O/petroleum ether); mp 98–100 °C (petroleum
ether) [Lit.43 93–94 °C (CCl4)].
(±)-anti-1-(4-Methylphenyl)-2-phenylbut-3-en-1-ol (3c)
The title compound was prepared according to general procedure 1
from p-tolualdehyde (42.3 mg, 0.352 mmol) and boronic ester 2 (99.7
mg, 0.408 mmol). The crude material was purified by flash chroma-
tography (10% Et2O/petroleum ether) to give alcohol 3c (67.4 mg,
80%) as a colourless oil.
1H NMR (400 MHz, CDCl3):  = 7.50–7.48 (m, 2 H, ArH), 7.26–7.19 (m,
5 H, ArH), 7.04–7.02 (m, 2 H, ArH), 6.23 (dt, J = 17.1, 9.7 Hz, 1 H,
CH=CH2), 5.34–5.25 (m, 2 H, CH=CH2), 4.87 (d, J = 7.9 Hz, 1 H, HOCH),
3.46 (dd, J = 9.7, 7.9 Hz, 1 H, C=CCH), 2.48 (s, 1 H, OH).
13C NMR (101 MHz, CDCl3):  = 147.1 (C), 139.6 (C), 136.9 (CH), 131.7
(2 × CH), 128.7 (2 × CH), 128.1 (2 × CH), 127.3 (2 × CH), 127.1 (CH),
119.4 (CH2), 118.8 (C), 111.1 (C), 76.6 (CH), 59.5 (CH).
Rf = 0.16 (10% Et2O/n-hexane).
IR (ATR): 3437 (O–H), 3025, 1636, 1492, 1178, 915, 755 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.25–7.14 (m, 3 H, ArH), 7.09–7.01 (m,
6 H, ArH), 6.26 (ddd, J = 17.1, 10.2, 9.1 Hz, 1 H, CH=CH2), 5.28 (d,
J = 10.2 Hz, 1 H, CH=CHAHB), 5.22 (d, J = 17.1 Hz, 1 H, CH=CHAHB), 4.84
(d, J = 7.8 Hz, 1 H, HOCH), 3.57 (dd, J = 9.1, 7.8 Hz, 1 H, C=CCH), 2.29 (s,
3 H, CH3).
13C NMR (100 MHz, CDCl3):  = 140.8 (C), 138.8 (C), 138.0 (CH), 137.0
(C), 128.6 (2 × CH), 128.3 (3 × CH), 126.6 (2 × CH), 126.5 (2 × CH),
118.2 (CH2), 77.0 (CH), 59.1 (CH), 21.1 (CH3).
For X-ray crystallography data, see the Supporting Information.
(±)-anti-1-(4-Trifluoromethylphenyl)-2-phenylbut-3-en-1-ol (3g)
The title compound was prepared according to general procedure 1
from 4-(trifluoromethyl)benzaldehyde (55.2 mg, 0.317 mmol) and
boronic ester 2 (104 mg, 0.426 mmol). The crude material was puri-
fied by flash chromatography (10% Et2O/n-hexane) to give alcohol 3g
(88.3 mg, 95%) as a pale yellow oil. The data are consistent with the
literature.41
HRMS (ESI): m/z [M + Na]+ calcd for C17H18ONa: 261.1250; found:
261.1246.
Rf = 0.16 (10% Et2O/n-hexane).
1H NMR (400 MHz, CDCl3):  = 7.47 (d, J = 8.1 Hz, 2 H, ArH), 7.27–7.19
(m, 5 H, ArH), 7.10–7.05 (m, 2 H, ArH), 6.25 (ddd, J = 17.1, 10.2, 9.0 Hz,
1 H, CH=CH2), 5.36–5.21 (m, 2 H, CH=CH2), 4.91 (dd, J = 7.7, 2.1 Hz, 1
H, HOCH), 3.52 (dd, J = 9.0, 7.7 Hz, 1 H, C=CCH), 2.40 (d, J = 2.1 Hz, 1 H,
OH).
13C NMR (101 MHz, CDCl3):  = 145.7 (C), 145.7 (C), 139.9 (CH), 137.2
(CH), 129.5 (C, q, JC–F = 32.3 Hz), 128.6 (2 × CH), 128.2 (2 × CH), 127.0
(2 × CH), 124.8 (2 × CH, q, JC–F = 3.8 Hz), 123.7 (CF3, br q, JC–F = 272.4
Hz), 119.1 (CH2), 76.6 (CH), 59.3 (CH).
(±)-anti-1,2-Diphenylbut-3-en-1-ol (3d)
The title compound was prepared according to general procedure 1
from benzaldehyde (37.0 mg, 0.349 mmol) and boronic ester 2 (101
mg, 0.414 mmol). The crude material was purified by flash chroma-
tography (10% Et2O/petroleum ether) to give alcohol 3d (54.4 mg,
70%) as a colourless oil. The data are consistent with the literature.41
Rf = 0.16 (10% Et2O/petroleum ether).
1H NMR (400 MHz, CDCl3):  = 7.25–7.14 (m, 8 H, ArH), 7.08–7.06 (m,
2 H, ArH), 6.27 (ddd, J = 17.2, 10.3, 8.4 Hz, 1 H, CH=CH2), 5.30–5.22 (m,
2 H, CH=CH2), 4.87 (d, J = 7.8 Hz, 1 H, HOCH), 3.57 (dd, J = 8.4, 7.8 Hz, 1
H, C=CCH), 2.30 (d, J = 2.3 Hz, 1 H, OH).
© 2020. Thieme. All rights reserved. Synthesis 2020, 52, A–L

I
F. M. Dennis et al.
Paper
Synthesis
(±)-anti-1-(3-Methoxyphenyl)-2-phenylbut-3-en-1-ol (3h)
(±)-anti-1-(2-Fluorophenyl)-2-phenylbut-3-en-1-ol (3k)
The title compound was prepared according to general procedure 1
from m-anisaldehyde (44.7 mg, 0.328 mmol) and boronic ester 2
(101.0 mg, 0.414 mmol). The crude material was purified by flash
chromatography (10% Et2O/n-hexane) to give alcohol 3h (70.5 mg,
84%) as a colourless oil. The data are consistent with the literature.41
The title compound was prepared according to general procedure 1
from 2-fluorobenzaldehyde (41.3 mg, 0.333 mmol) and boronic ester
2 (97.2 mg, 0.398 mmol). The crude material was purified by flash
chromatography (10% Et2O/petroleum ether) to give alcohol 3k (66.4
mg, 82%) as a pale yellow oil.
Rf = 0.07 (10% Et2O/n-hexane).
Rf = 0.16 (10% Et2O/petroleum ether).
1H NMR (400 MHz, CDCl3):  = 7.23–7.16 (m, 2 H, ArH), 7.12–7.08 (m,
4 H, ArH), 6.75–6.70 (m, 3 H, ArH), 6.26 (ddd, J = 17.1, 10.2, 8.9 Hz, 1
H, CH=CH2), 5.30–5.21 (m, 2 H, CH=CH2), 4.84 (dd, J = 7.6, 2.5 Hz, 1 H,
HOCH), 3.71 (s, 3 H, CH3), 3.54 (dd, J = 8.9, 7.6 Hz, 1 H, C=CCH), 2.29 (d,
J = 2.5 Hz, 1 H, OH).
13C NMR (126 MHz, CDCl3):  = 159.2 (C), 143.5 (C), 140.6 (C), 137.8
(CH), 128.9 (CH), 128.3 (4 × CH), 126.6 (CH), 119.0 (CH), 118.4 (CH2),
113.2 (CH), 111.9 (CH), 77.3 (CH), 59.1 (CH), 55.1 (CH3).
IR (ATR): 3411 (O–H), 2915, 1489, 1221, 1030, 918, 796 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.40 (td, J = 13.2, 2.7 Hz, 1 H, ArH),
7.24–7.19 (m, 6 H, ArH), 7.08 (td, J = 7.5, 2.5 Hz, 1 H, ArH), 6.91–6.87
(m, 1 H, ArH), 6.29–6.23 (m, 1 H, CH=CH2), 5.26–5.23 (m, 2 H,
CH=CHAHB and HOCH), 5.16 (dd, J = 17.7, 1.7 Hz, 1 H, CH=CHAHB), 3.69
(dd, J = 8.2, 7.8 Hz, 1 H, C=CCH), 2.25 (br s, 1 H, OH).
13C NMR (101 MHz, CDCl3):  = 159.8 (d, JC–F = 245.6 Hz, C), 140.5 (C),
137.2 (C), 129.1 (d, JC–F = 12.8 Hz, CH), 128.9 (d, JC–F = 8.4 Hz, CH),
128.4 (2 × CH), 128.3 (d, JC–F = 4.4 Hz, CH), 128.2 (2 × CH), 126.7 (CH),
123.9 (d, JC–F = 3.4 Hz, CH), 118.5 (CH2), 115.0 (d, JC–F = 22.1 Hz, CH),
71.2 (CH), 57.5 (CH).
(±)-anti-1-(3-Cyanophenyl)-2-phenylbut-3-en-1-ol (3i)
The title compound was prepared according to general procedure 1
from 3-cyanobenzaldehyde (45.3 mg, 0.345 mmol) and boronic ester
2 (99.3 mg, 0.407 mmol). The crude material was purified by flash
chromatography (10% Et2O/petroleum ether) to give alcohol 3i (67.3
mg, 78%) as a colourless oil.
19F NMR (377 MHz, CDCl3):  = –118.5 (s).
HRMS (EI): m/z [M]+ calcd for C16H15FO: 242.1101; found: 242.1112.
(±)-anti-1-(2-Nitrophenyl)-2-phenylbut-3-en-1-ol (3l)
Rf = 0.08 (10% Et2O/petroleum ether).
The title compound was prepared according to general procedure 1
from 2-nitrobenzaldehyde (50.2 mg, 0.332 mmol) and boronic ester 2
(98.6 mg, 0.404 mmol). The crude material was purified by flash
chromatography (10% Et2O/n-hexane) to give alcohol 3l (70.4 mg,
79%) as a colourless oil. The data are consistent with the literature.41
IR (ATR): 3450 (O–H), 2230 (C≡N), 1600, 1493, 920, 799 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.49–7.45 (m, 2 H, ArH), 7.31–7.22 (m,
5 H, ArH), 7.04–7.02 (m, 2 H, ArH), 6.23 (dt, J = 17.1, 9.7 Hz, 1 H,
CH=CH2), 5.35–5.25 (m, 2 H, CH=CH2), 4.86 (d, J = 7.9 Hz, 1 H, HOCH),
3.46 (dd, J = 9.7, 7.9 Hz, 1 H, C=CCH), 2.46 (s, 1 H, OH).
Rf = 0.23 (10% Et2O/petroleum ether).
13C NMR (126 MHz, CDCl3):  = 143.2 (C), 139.5 (C), 136.9 (CH),
131.12 (CH), 131.07 (CH), 130.3 (CH), 128.7 (2 × CH), 128.6 (CH),
128.1 (2 × CH), 127.1 (CH), 119.5 (CH2), 118.8 (C), 111.9 (C), 76.3 (CH),
59.6 (CH).
HRMS (ESI): m/z [M + H]+ calcd for C17H16NO: 250.1226; found:
250.1231.
1H NMR (400 MHz, CDCl3):  = 7.84 (dd, J = 8.2, 1.2 Hz, 1 H, ArH),
7.76–7.75 (m, 1 H, ArH), 7.58 (dd, J = 11.0, 4.2 Hz, 1 H, ArH), 7.40–7.34
(m, 1 H, ArH), 7.31–7.20 (m, 5 H, ArH), 6.37–6.28 (m, 1 H, CH=CH),
5.64 (d, J = 5.3 Hz, 1 H, HOCH), 5.20 (dd, J = 10.2, 1.0 Hz, 1 H,
CH=CHAHB), 5.03 (dd, J = 17.1, 1.0 Hz, 1 H, CH=CHAHB), 3.75 (dd, J = 9.2,
5.3 Hz, 1 H, C=CCH), 2.38 (s, 1 H, OH).
13C NMR (101 MHz, CDCl3):  = 148.0 (C), 140.7 (C), 137.3 (C), 135.7
(CH), 132.8 (CH), 129.4 (CH), 128.7 (2 × CH), 128.1 (3 × CH), 127.0
(CH), 124.3 (CH), 119.1 (CH2), 72.6 (CH), 56.7 (CH).
(±)-anti-1-(2-Methylphenyl)-2-phenylbut-3-en-1-ol (3j)
The title compound was prepared according to general procedure 1
from o-tolualdehyde (41.3 mg, 0.344 mmol) and boronic ester 2 (97.8
mg, 0.401 mmol). The crude material was purified by flash chroma-
tography (10% Et2O/petroleum ether) to give alcohol 3j (58.0 mg, 71%)
as a colourless oil.
(±)-anti-1-(1-Naphthyl)-2-phenylbut-3-en-1-ol (3m)
The title compound was prepared according to general procedure 1
from 1-napthaldehyde (50.5 mg, 0.324 mmol) and boronic ester 2
(99.0 mg, 0.406 mmol). The crude material was purified by flash
chromatography (10% Et2O/petroleum ether) to give alcohol 3m (75.8
mg, 85%) as a pale yellow oil. The data are consistent with the litera-
ture.44
Rf = 0.16 (10% Et2O/petroleum ether).
IR (ATR): 3416 (O–H), 2920, 1600, 1452, 1178, 918, 760 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.49 (d, J = 7.7 Hz, 1 H, ArH), 7.23–7.16
(m, 7 H, ArH), 6.99 (d, J = 7.5 Hz, 1 H, ArH), 6.35 (ddd, J = 17.1, 10.2, 8.9
Hz, 1 H, CH=CH2), 5.30 (dd, J = 10.2, 1.2 Hz, 1 H, CH=CHAHB), 5.20 (dd,
J = 17.1, 1.2 Hz, 1 H, CH=CHAHB), 5.12 (d, J = 7.1 Hz, 1 H, HOCH), 3.62
(dd, J = 8.9, 7.1 Hz, 1 H, C=CCH), 2.06 (s, 3 H, CH3).
13C NMR (101 MHz, CDCl3):  = 140.8 (C), 140.2 (C), 137.3 (CH), 135.1
(C), 130.0 (CH), 128.3 (4 × CH), 127.2 (CH), 126.6 (CH), 126.5 (CH),
125.8 (CH), 118.6 (CH2), 73.1 (CH), 57.7 (CH), 19.1 (CH3).
Rf = 0.16 (10% Et2O/petroleum ether).
1H NMR (400 MHz, CDCl3):  = 8.10 (d, J = 7.7 Hz, 1 H, ArH), 7.87–7.85
(m, 1 H, ArH), 7.75 (d, J = 8.1 Hz, 1 H, ArH), 7.56–7.40 (m, 4 H, ArH),
7.27–7.23 (m, 4 H, ArH), 7.20–7.16 (m, 1 H, ArH), 6.37–6.28 (m, 1 H,
CH=CH2), 5.73–5.71 (m, 1 H, HOCH), 5.22 (d, J = 10.3 Hz, 1 H,
CH=CHAHB), 5.00 (d, J = 17.2 Hz, 1 H, CH=CHAHB), 3.94 (dd, J = 8.4, 5.5
Hz, 1 H, C=CCH), 2.30 (d, J = 3.2 Hz, 1 H, OH).
13C NMR (101 MHz, CDCl3):  = 141.6 (C), 137.7 (CH), 136.7 (C), 133.7
(C), 130.5 (C), 128.9 (CH), 128.5 (2 × CH), 128.2 (2 × CH), 128.0 (CH),
126.7 (CH), 125.9 (CH), 125.3 (CH), 125.0 (CH), 124.5 (CH), 123.1 (CH),
118.6 (CH2), 74.2 (CH), 56.6 (CH).
HRMS (ESI): m/z [M + H]+ calcd for C17H18ONa: 261.1250; found:
261.1250.
© 2020. Thieme. All rights reserved. Synthesis 2020, 52, A–L

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F. M. Dennis et al.
Paper
Synthesis
(±)-anti-2-phenyl-1-(Pyridine-2-yl)but-3-en-1-ol (3n)
flash chromatography (10% Et2O/petroleum ether) to give alcohol 3q
(57.2 mg, 69%) as a colourless oil. The data are consistent with the lit-
erature.45
The title compound was prepared according to general procedure 1
from 2-pyridinecarboxaldehyde (35.7 mg, 0.333 mmol) and boronic
ester 2 (95.0 mg, 0.389 mmol). The crude material was purified by
flash chromatography (10% Et2O/petroleum ether) to give alcohol 3n
(52.0 mg, 69%) as a pale yellow oil.
Rf = 0.23 (10% Et2O/petroleum ether).
1H NMR (400 MHz, CDCl3):  = 7.32 (t, J = 7.3 Hz, 2 H, ArH), 7.27–7.22
(m, 3 H, ArH), 7.18–7.17 (m, 3 H, ArH), 7.12 (d, J = 7.0 Hz, 2 H, ArH),
6.16–6.07 (m, 1 H, CH=CH2), 5.25 (dd, J = 10.2, 1.1 Hz, 1 H, CH=CHAHB),
5.22 (dd, J = 17.4, 1.1 Hz, 1 H, CH=CHAHB), 3.83–3.76 (m, 1 H, HOCH),
3.30–3.26 (m, 1 H, C=CCH), 2.88–2.81 (m, 1 H, PhCHAHB), 2.67–2.59
(m, 1 H, PhCHAHB), 1.88–1.86 (m, 1 H, PhCH2CHAHB), 1.70–1.61 (m, 1
H, PhCH2CHAHB), 1.58 (s, 1 H, OH).
13C NMR (126 MHz, CDCl3):  = 142.0 (C), 141.4 (C), 138.3 (CH), 128.7
(2 × CH), 128.4 (2 × CH), 128.3 (2 × CH), 128.0 (2 × CH), 126.7 (CH),
125.7 (CH), 118.0 (CH2), 73.2 (CH), 57.5 (CH), 36.0 (CH2), 32.0 (CH2).
Rf = 0.10 (10% Et2O/petroleum ether); mp 75–77 °C (petroleum ether).
IR (ATR): 3250 (O–H), 3080, 1598, 1433, 1066, 928, 756, 698 cm–1
.
1H NMR (400 MHz, CDCl3):  = 8.55 (d, J = 4.5 Hz, 1 H, ArH), 7.60–7.56
(m, 1 H, ArH), 7.29–7.19 (m, 6 H, ArH), 6.98 (d, J = 7.9 Hz, 1 H, ArH),
6.24 (ddd, J = 17.1, 10.3, 8.3 Hz, 1 H, CH=CH2), 5.16–5.13 (dd, J = 10.3,
1.2 Hz, 1 H, HOCH), 5.07–5.01 (m, 2 H, CH=CH2), 4.25 (br s, 1 H, OH),
3.78–3.71 (m, 1 H, C=CCH).
13C NMR (101 MHz, CDCl3):  = 160.0 (CH), 148.2 (C), 141.2 (C), 137.1
(CH), 136.1 (CH), 128.5 (2 × CH), 128.4 (2 × CH), 126.6 (CH), 122.4
(CH), 121.5 (CH), 117.6 (CH2), 76.2 (CH), 57.8 (CH).
(±)-anti-1-Cyclohexyl-2-phenylbut-3-en-1-ol (3r)
The title compound was prepared according to general procedure 1
from cyclohexane carboxaldehyde (38.9 mg, 0.347 mmol) and boronic
ester 2 (99.6 mg, 0.408 mmol). The crude material was purified by
flash column chromatography on silica gel (10% Et2O/n-hexane) to
give alcohol 3r (47.2 mg, 59%) as a colourless oil. The data are consis-
tent with the literature.46
HRMS (ESI): m/z [M + H]+ calcd for C15H16NO: 226.1226; found:
226.1230.
(±)-anti-1-(Furan-2-yl)-2-phenylbut-3-en-1-ol (3o)
The title compound was prepared according to general procedure 1
from furaldehyde (35.8 mg, 0.372 mmol) and boronic ester 2 (96.2
mg, 0.394 mmol). The crude material was purified by flash chroma-
tography (10% Et2O/petroleum ether) to give alcohol 3o (49.1 mg,
62%) as a pale yellow oil. The data are consistent with the literature.44
Rf = 0.10 (10% Et2O/n-hexane).
1H NMR (400 MHz, CDCl3):  = 7.35–7.32 (m, 2 H, ArH), 7.27–7.22 (m,
3 H, ArH), 6.15 (ddd, J = 17.0, 9.7, 8.7 Hz, 1 H, CH=CH2), 5.24–5.18 (m,
2 H, CH=CH2), 3.60–3.58 (m, 1 H, HOCH), 3.47 (dd, J = 8.7, 7.8 Hz, 1 H,
C=CCH), 1.83–1.82 (m, 1 H, Cy), 1.73–1.59 (m, 4 H, Cy), 1.27–1.01 (m,
6 H, Cy).
13C NMR (101 MHz, CDCl3):  = 142.1 (C), 138.4 (CH), 128.7 (2 × CH),
127.9 (2 × CH), 126.5 (CH), 117.7 (CH2), 78.1 (CH), 53.7 (CH), 39.5
(CH), 30.2 (CH2), 26.5 (CH2), 26.4 (CH2), 26.3 (CH2), 26.0 (CH2).
Rf = 0.16 (10% Et2O/petroleum ether).
1H NMR (400 MHz, CDCl3):  = 7.33–7.15 (m, 6 H, ArH), 6.25–6.20 (m,
2 H, ArH), 6.06 (ddd, J = 17.2, 10.2, 8.3 Hz, 1 H, CH=CH2), 5.31–5.25 (m,
2 H, CH=CH2), 4.90 (d, J = 8.3 Hz, 1 H, HOCH), 3.85 (t, J = 8.3 Hz, 1 H,
C=CCH), 2.27 (s, 1 H, OH).
13C NMR (101 MHz, CDCl3):  = 154.2 (C), 141.8 (CH), 140.4 (C), 137.6
(CH), 128.4 (2 × CH), 128.1 (2 × CH), 126.8 (CH), 118.5 (CH2), 110.1
(CH), 107.6 (CH), 71.0 (CH), 55.9 (CH).
(1S,2R)-1-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-2-phenylbut-3-
en-1-ol (3s)
The title compound was prepared according to general procedure 1
from 2,3-O-isopropylidene-D-glyceraldehyde (50% w/w in dichloro-
methane, 175.5 mg, 0.674 mmol) and boronic ester 2 (196.6 mg,
0.805 mmol). The crude material was purified by flash chromatogra-
phy (10% Et2O/petroleum ether) to give alcohol 3s (70.6 mg, 42%) as a
pale yellow solid.
(±)-anti-1-(3-Bromothiophen-2-yl)-2-phenylbut-3-en-1-ol (3p)
The title compound was prepared according to general procedure 1
from 3-bromothiophene-2-carboxaldehyde (63.9 mg, 0.334 mmol)
and boronic ester 2 (100.6 mg, 0.412 mmol). The crude material was
purified by flash chromatography (10% Et2O/pentane) to give alcohol
3p (83.0 mg, 80%) as a colourless oil.
[]D20 +82 (c = 0.22, CHCl3); mp 54–56 °C (pentane).
Rf = 0.33 (10% Et2O/pentane).
IR (ATR): 3484 (O–H), 2993, 1455, 1221, 1061, 698 cm–1
.
IR (ATR): 3414 (O–H), 3038, 2904, 1601, 1494, 920, 870, 698 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.35–7.32 (m, 2 H, ArH), 7.26–7.24 (m,
3 H, ArH), 6.25 (ddd, J = 17.2, 10.2, 8.5 Hz, 1 H, CH=CH2), 5.21 (d, J = 9.6
Hz, 1 H, CH=CHAHB), 5.15 (d, J = 17.1 Hz, 1 H, CH=CHAHB), 3.92 (td,
J = 6.7, 4.8 Hz, 1 H, OCHCH2), 3.77–3.70 (m, 2 H, OCHcHd + CHOH),
3.62 (t, J = 7.6 Hz, 1 H, OCHcHd), 3.39 (t, J = 8.1 Hz, 1 H, CHPh), 2.31 (d,
J = 5.8 Hz, 1 H, OH), 1.44 (s, 3 H, CH3), 1.31 (s, 3 H, CH3).
13C NMR (101 MHz, CDCl3):  = 140.8 (C), 138.1 (CH), 128.7 (2 × CH),
128.3 (2 × CH), 126.9 (CH), 117.2 (CH2), 109.1 (C), 76.5 (CH), 74.4
(CH), 66.1 (CH2), 54.1 (CH), 26.5 (CH3), 25.3 (CH3).
1H NMR (400 MHz, CDCl3):  = 7.29–7.20 (m, 6 H, ArH), 6.81 (d, J = 5.3
Hz, 1 H, ArH), 6.31 (ddd, J = 17.1, 10.2, 8.9 Hz, 1 H, CH=CH2), 5.30–5.28
(m, 2 H, C=CHACHB, HOCH), 5.26–5.21 (m, 1 H, C=CHACHB), 3.78–3.70
(m, 1 H, C=CCH), 2.44 (d, J = 2.9 Hz, 1 H, OH).
13C NMR (126 MHz, CDCl3):  = 140.3 (C), 139.9 (C), 136.8 (CH), 129.5
(CH), 128.5 (2 × CH), 128.2 (2 × CH), 126.9 (CH), 125.1 (CH), 119.0
(CH2), 108.6 (C), 72.4 (CH), 57.9 (CH).
HRMS (ESI): m/z [M + Na]+ calcd for C14H1381BrOSNa: 332.9742;
HRMS (Q-TOF): m/z [M + H]+ calcd for C15H21O3: 249.1446; found:
found: 332.9742.
249.1485.
(±)-anti-1,4-Diphenylhex-5-en-3-ol (3q)
For X-ray crystallography data, see the Supporting Information.
The title compound was prepared according to general procedure 1
from 3-phenylpropionaldehyde (44.2 mg, 0.329 mmol) and boronic
ester 2 (97.3 mg, 0.399 mmol). The crude material was purified by
© 2020. Thieme. All rights reserved. Synthesis 2020, 52, A–L

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F. M. Dennis et al.
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Funding Information
(13) For selected reviews on allylboration, see: (a) Jonnalagadda, S.
C.; Suman, P.; Patel, A.; Jampana, G.; Colfer, A. Allylboration, In
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2011, 111, 7774.
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787. (b) Hegedus, L. S.; Wagner, S. D.; Waterman, E. L.; Siirala-
Hansen, K. J. Org. Chem. 1975, 40, 593. (c) Baker, R. Chem. Rev.
1973, 73, 487.
This work was supported by the University of Sheffield and the Engi-
neering and Physical Sciences Research Council (EPSRC).
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Supporting Information
Supporting information for this article is available online at
https://doi.org/10.1055/s-0039-1690091.
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