Facile synthesis of (Z)-anti-homoallylic alcohols from 3-(pinacolatoboryl)allyl alcohols, aldehydes, and triorganoboranes via a palladium-catalyzed three-component reaction

Article abstract of DOI:10.1016/j.tetlet.2016.06.121

A palladium-catalyzed three-component reaction of 3-(pinacolatoboryl)allyl alcohols, aldehydes, and triorganoboranes was developed. The present protocol provides facile access to synthetically useful (Z)-anti-homoallylic alcohols with high diastereoselect

Full text of DOI:10.1016/j.tetlet.2016.06.121

Accepted Manuscript
Facile Synthesis of (Z)-anti-Homoallylic Alcohols from 3-(Pinacolatoboryl)all-
yl Alcohols, Aldehydes, and Triorganoboranes via a Palladium-Catalyzed
Three-Component Reaction
Yoshikazu Horino, Ataru Aimono, Naoki Minoshima, Hitoshi Abe
PII:
S0040-4039(16)30800-0
DOI:
http://dx.doi.org/10.1016/j.tetlet.2016.06.121
TETL 47848
Reference:
Tetrahedron Letters
To appear in:
Received Date:
Revised Date:
Accepted Date:
8 May 2016
22 June 2016
27 June 2016
Please cite this article as: Horino, Y., Aimono, A., Minoshima, N., Abe, H., Facile Synthesis of (Z)-anti-Homoallylic
Alcohols from 3-(Pinacolatoboryl)allyl Alcohols, Aldehydes, and Triorganoboranes via a Palladium-Catalyzed
Three-Component Reaction, Tetrahedron Letters (2016), doi: http://dx.doi.org/10.1016/j.tetlet.2016.06.121
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Facile Synthesis of (Z)-anti-Homoallylic
Alcohols from 3-(Pinacolatoboryl)allyl
Alcohols, Aldehydes, and Triorganoboranes
via a Palladium-Catalyzed Three-
Component Reaction
Leave this area blank for abstract info.
Yoshikazu Horino, Ataru Aimono, Naoki Minoshima, and Hitoshi Abe
OH
R1
Pd(OAc)2 (10 mol%)
PCyPh2 (20 mol%)
OH
(R3)3B
R2CHO
B(pin)
R2
+
+
toluene, 50 °C
R1 R3

1
Tetrahedron Letters
Facile Synthesis of (Z)-anti-Homoallylic Alcohols from 3-(Pinacolatoboryl)allyl
Alcohols, Aldehydes, and Triorganoboranes via a Palladium-Catalyzed Three-
Component Reaction
Yoshikazu Horino, Ataru Aimono, Naoki Minoshima, and Hitoshi Abe
Department of Applied Chemistry, Graduate School of Science and Engineering, University of Toyama, Gofuku, Toyama 930-8555, Japan
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
A palladium-catalyzed three-component reaction of 3-(pinacolatoboryl)allyl alcohols, aldehydes,
and triorganoboranes was developed. The present protocol provides facile access to synthetically
useful (Z)-anti-homoallylic alcohols with high diastereoselectivity and high levels of alkene
stereocontrol. Furthermore, a single synthetic-step operation to synthesize (Z)-anti-homoallylic
alcohols starting from propargyl alcohols by using palladium-catalyzed three-component
reaction is successfully achieved.
Available online
2016 Elsevier Ltd. All rights reserved.
Keywords:
Allylation
Three-component reaction
Palladium catalysis
Homoallylic alcohols
aldehydes, and an acetoxy group on the palladium atom acts as a
Lewis base to intramolecularly activate the pinacolatoboryl group
Introduction
Recent advances have greatly increased the utility of allylic
alcohols as allylating reagents in the σ-allylpalladium-mediated
nucleophilic allylation reactions. These reactions differ from
hitherto reported umpolung methods wherein π-allylpalladium
complexes are used.1-4 For instance, Zhou and co-workers applied
Tamaru’s umpolung allylation protocol,5 wherein allylic alcohols
are used as allylating reagents, to the palladium-catalyzed
asymmetric umpolung allylation of carbonyl compounds and
imines, wherein σ-allylpalladium intermediates generated from
the triethylborane-mediated umpolung reaction of π-
allylpalladium were proposed to serve as nucleophiles.1
Furthermore, Sato and Mita have reported the σ-allylpalladium-
mediated carboxylation of allylic alcohols with CO2 in the
presence of ZnEt2.6 These studies indicate the utility of a route to
σ-allylpalladium-mediated nucleophilic allylation products using
allylic alcohols as allylating reagents. However, a simple and
convenient method for directly using allylic alcohols as allylating
reagents is still highly desired from a step- and atom-economic
point of view.7
at the α-position. As a result, the nucleophilic allylation of
aldehydes with allylboronates takes place via a putative cis-
decaline-like cyclic transition state; the resulting vinylpalladium
intermediates couple with triorganoboranes to give (Z)-anti-
homoallylic alcohols. In mechanistic studies, we found that 3-
(pinacolatoboryl)allyl alcohol 1a was also able to take part in the
palladium-catalyzed three-component reaction (Scheme 1b).
However, the desired product 4aaa was obtained in only
moderate yield with a significant amount of the β-hydride
elimination product 5aa. As an effort toward the developing an
atom-economical nucleophilic allylation reaction utilizing allylic
alcohols as allylating reagents,9 we herein report the facile
synthesis of (Z)-anti-
Pd(OAc)2
PCyPh2
OAc
OH
R1
B(pin)
R2CHO
(R3)3B
+
R2
+
(a)
THF, 50 ºC
R1
OH
R3
Ph
We have previously reported the palladium-catalyzed three-
component reaction of 3-(pinacolatoboryl)allyl acetates,
aldehydes, and triorganoboranes that stereoselectively provides
(Z)-anti-homoallylic alcohols (Scheme 1a).8 Although the
reaction also proceeds via σ-allylpalladium intermediates, the
reaction mechanism is different from the protocols mentioned
above; the palladium atom in the formation of σ-allylpalladium
Ph Et
OH
4aaa (53%)
as above
Et3B
+
PhCHO
+
+
OH
(b)
Ph
B(pin)
THF, 50 °C
1a
2a
3a
Ph
Ph
5aa (11%)
intermediates serves as a Lewis acid to coordinate with
———
 Corresponding author. Tel.: +81-76-445-6820; fax: +81-76-445-6820; e-mail: horino@eng.u-toyama.ac.jp

2
Tetrahedron
Scheme 1. Previous works
reaction condition, to our delight, 4aja was formed in 70% yield
when the amount of 3a was increased. On the other hand,
homoallylic alcohols from 3-(pinacolatoboryl)allyl alcohols,
aldehydes, and triorganoboranes via a palladium-catalyzed three-
component reaction. It is worth noting that (Z)-anti-homoallylic
alcohols cannot be easily accessed via known catalytic
conditions.10-12
Table 2. Scope of Aldehydesa
OH
R
Pd(OAc)2 (10 mol%)
Ph Et
OH
Results and discussion
PCyPh2 (20 mol%)
4
Et3B
+ RCHO
+
+
Ph
B(pin)
Initially, we screened the reaction conditions for the
toluene, 50 °C
OH
1a
2
3a
palladium-catalyzed
three-component
reaction
of
1a,
R
benzaldehyde (2a), and triethylborane (3a) by evaluating various
ligands (Table 1). The reaction of 1a (1 equiv), 2a (2.4 equiv),
and 3a (2.4 equiv) in the presence of Pd(OAc)2 (10 mol%) and
PCyPh2 (20 mol%) in toluene under Ar atmosphere at 50 ºC
afforded the corresponding product 4aaa in 52% isolated yield
along with 5aa in 9% yield (entry 1). The chemical yield of 4aaa
and the ratio of 4aaa/5aa improved when the 3.6 equivalents of
triethylborane was used (entry 2). However, further addition of
triethylborane did not ameliorate the reaction (entry 3). Among
the monodentate phosphine ligand tested, PCyPh2 showed the
best result in terms of chemical yield of 4aaa and the ratio of
4aaa/5aa (entries 4–7). Moreover, changing the palladium source
from Pd(OAc)2 to Pd2(dba)3CHCl3 did not efficiently promote the
present reaction (entry 8).
Ph
5
OH
OH
MeO
OH
MeO
Ph Et
Ph Et
Ph Et
MeO
4aba (83%, dr >99:1)
4/5 = 17/1
4aca (72%, dr >99:1)
4/5 = 9/1
4ada (76%, dr >99:1)
4/5 = 24/1
OH
OH
OH
O
Ph Et
O
Ph Et
Ph Et
MeO2C
F3C
4aea (79%, dr >99:1)
4/5 = 5/1
4afa (71%, dr >99:1)
4/5 = 12/1
4aga (72%, dr >99:1)
4/5 = 12/1
OH
OH
OH
Table 1. Optimization of reaction conditionsa
O
Ph Et
Ph Et
Ph Et
OH
Ph
X
HO
4aja (70%)b
4/5 = >30/1
4aha (X = Cl, 61%)
4/5 = 9/1
4aka (68%, dr = 98:2)
4/5 = 6/1
Pd(OAc)2
Ligand
4aia (X = Br, 0%)b
Ph Et
OH
4aaa
OH
S
OH
OH
Et3B
+
PhCHO
+
+
OH
Ph
B(pin)
toluene, 50 °C
1a
2a
3a
Ph Et
Ph Et
Ph Et
Ph
Ph
5aa
4ala (78%, dr = 97:3)
4/5 = 20/1
4ama (55%, dr >99:1)
4/5 = 28/1
4ana (42%, dr >99:1)
4/5 = 5/1
Entry
Ligand
Time
(h)
4aaa
Z/Ec
5aa
(%)b
52
60
51
35
52
54
57
58
(%)b
a Conditions: 1a (0.5 mmol), 2 (1.2 mmol), 3a (1 M in hexane sol., 1.8 mmol),
Pd(OAc)2 (0.05 mmol), and PCyPh2 (0.1 mmol) in toluene (2 mL) at 50 °C.
b 3a (1 M in hexane sol., 2.4 mmol) was used.
1d
2
PCyPh2
PCyPh2
PCyPh2
P(n-Bu)3
PPh3
4
>20/1
>20/1
>20/1
>20/1
>20/1
>20/1
>20/1
>20/1
9
4
6
3e
4
7
2i did not take part in the reaction. Furthermore, we investigated
the reaction of heterocyclic aldehydes and observed that the
reactions of furfural and 2-thienylaldehydes smoothly proceeded
to produce 4aka and 4ala, respectively, in good yields.
Nevertheless, it is noteworthy that the aliphatic aldehydes such as
isobutyraldehyde (2m) and cyclohexanecarbaldehyde (2n)
successfully participated in the reaction to produce 4ama and
4ana in 55% and 42% yields, respectively. The high
diastereoselectivity and high levels of alkene stereocontrol were
observed for all aldehydes examined.
4
5
31
17
14
7
5
4.5
4.5
7
6
P(p-MeOC6H4)3
P(p-CF3C6H4)3
PCyPh2
7
8f
6
4
a Conditions: 1a (0.5 mmol), 2a (1.2 mmol), 3a (1 M in hexane sol., 1.8
mmol), Pd(OAc)2 (0.05 mmol), and PCyPh2 (0.1 mmol) in toluene (2 mL) at
50 °C.
b Isolated yield.
Next, the three-component reaction was applied to 3-
(pinacolatoboryl)allyl alcohol 1 having various simple or
functionalized aryl substituents using 2a and 3a (Table 3). 3-
(Pinacolatoboryl)allyl alcohols possessing an electron-
withdrawing group on the aromatic ring afforded 4baa, 4caa, and
4daa in 62%–65% yields. Conversely, an electron-donating
group on the aromatic ring resulted in decreased yields, giving
4eaa in 39% yield with a significant amount of β-hydride
elimination product 5ea. In addition, when heteroaryl-substituted
substrates were subjected to the reaction, the reaction time
required to achieve full conversion was longer, providing 4faa
and 4gaa in 68% and 40% yields, respectively. In contrast to our
previous study,8 the present protocol is not applicable to 3-
c The ratio of Z/E was determined by NMR analysis of the crude mixtures.
d 3a (1 M in hexane sol., 1.2 mmol) was used.
e 3a (1 M in hexane sol., 2.4 mmol) was used.
f Pd2(dba)3CHCl3 (5 mol%) and PCyPh2 (20 mol%) were used.
Having determined the optimal conditions, we subsequently
explored the reaction scope using various aldehydes and 1a and
3a (Table 2). It was found that a wide array of electronically and
sterically diverse aromatic aldehydes 2b–2h was tolerant to
produce 4aba–4aha in good-to-high yields with high
diastereoselectivities and high levels of alkene stereocontrol.
While p-bromobenzaldehyde (2i) and p-hydroxybenzaldehyde
(2j) did not afford the corresponding products under optimized
(pinacolatoboryl)allyl alcohol having
a
p-bromophenyl

3
a Conditions: 1 (0.5 mmol), 2a (1.2 mmol), 3 (1.8 mmol), Pd(OAc)2 (0.05
mmol), and PCyPh2 (0.1 mmol) in toluene (2 mL) at 50 °C.
b Reaction was performed at 80 °C.
substituent. In the case of methyl-substituted substrate 1i, the
reaction smoothly proceeded to provide 4iaa in 58% yield. The
Table 3. Scope of Substratesa
Pd(OAc)2 (10 mol%)
PCyPh2 (20 mol%)
OH
HB(pin)
(3 mmol)
H2O
(2.4 mmol)
Et3B (3.6 mmol)
ArCHO (2.4 mmol)
OH
Ph
Pd(OAc)2 (10 mol%)
PCyPh2 (20 mol%)
R
Et
4
OH
Ph
toluene (4 mL)
50 ºC, 4 h
neat, 150 ºC THF (2 mL)
overnight r.t., 1 h
Et3B
+ PhCHO +
+
R
B(pin)
6 (1 mmol)
toluene, 50 °C
OH
1
2a
3a
OH
OH
Ph
Ph
R
5
Ph Et
R
R
HO
Ph
HO
HO
4aba (R = MeO, 60%, dr >99:1)
4afa (R = CO2Me, 52%, dr >99:1)
4aga (R = CF3, 50%, dr >99:1)
5ab (R = MeO, 16%, dr >99:1)
5af (R = CO2Me, 8%, dr >99:1)
5ag (R = CF3, 4%, dr >99:1)
Et
Et
Et
Ph
Ph
OMe
CF3
CO2Me
4baa
(3 h, 62%, dr >99:1)
4caa
4daa
(8 h, 62%, dr >99:1)
Pd(OAc)2 (10 mol%)
PCyPh2 (20 mol%)
Et3B (3.6 mmol)
PhCHO (2.4 mmol)
4aaa
(3 h, 65%, dr >99:1)
4/5 = 8/1
4/5 = >20/1
4/5 = 10/1
HB(pin)
(3 mmol)
H2O
(2.4 mmol)
HO
HO
HO
(R)-6
(99% ee,
1 mmol)
Et
Et
Et
neat, 150 ºC THF (2 mL)
overnight
toluene (4 mL)
(49%, dr >99:1,
Ph
Ph
S
Ph
r.t., 1 h
50 ºC, 4 h
4% ee)
O
Scheme 2. A single synthetic-step operation via hydroboration/three-
OMe
4eaa
4faa
4gaa
component reaction
(3 h, 39%, dr >99:1)
(8h, 68%, dr >99:1)
17/1 = 17/1
(12 h, 40%, dr >99:1)
4/5 = 10/1
4/5 = 3/1
HO
HO
Ph
HO
the three-component reaction to give 4aab and 4cac in 53% and
55% yields, respectively, with high diastereo- and (Z)-selectivity.
In addition, the commercially available tri-n-butylborane
afforded 4aad in 55% yield with high Z-selectivity. As a
limitation, triphenylborane, tri-sec-alkylboranes, B-alkyl-9-BBN,
and alkyl boronate esters are not suitable coupling partners at the
current level of development.
Et
Et
Et
Ph
Me
4iaa
Ph
4jaa
(1 h, 58%, dr >99:1)b (24 h, 40%, dr >99:1)b,c
Br
4/5 = 12/1
4/5 = >20/1
4haa (0%)
a Conditions: 1 (0.5 mmol), 2a (1.2 mmol), 3a (1 M in hexane sol., 1.8 mmol),
Pd(OAc)2 (0.05 mmol), and PCyPh2 (0.1 mmol) in toluene (2 mL) at 50 °C.
b Reaction was performed at 70 °C.
Finally, we examined a single synthetic-step operation to
synthesize (Z)-anti-homoallylic alcohols starting from propargyl
alcohols by using palladium-catalyzed three-component reaction
(Scheme 2).13 Propargyl alcohol 6 was treated with pinacolborane
at 150 °C for 12 h. H2O and THF were then added, and the
mixture was stirred at room temperature for 1 h. After the volatile
materials were removed under reduced pressure, p-anisaldehyde,
a toluene solution of the prepared Pd-PCyPh2 catalyst, and Et3B
(1 M in hexane) were successively added to the residue. The
reaction was completed in 4 h, and the corresponding (Z)-anti-
homoallylic alcohol 4aba was obtained in 60% isolated yield
along with 5ab in 16%. Similarly, the present sequential
procedure allowed the use of p-(trifluoromethyl)benzaldehyde
and methyl 4-formylbenzoate to give 4afa and 4aga,
respectively, in good overall yields. Next, a chirality transfer
experiment was examined using (R)-6 in a single synthetic-step
operation. In contrast to our previous work,8 an efficient chirality
transfer was not observed, and 4aaa was produced in 49% yield
as a nearly racemic mixture.14 In all cases, high levels of (Z)-
stereo- and diastereoselectivity were observed.
c Pd(OAc)2 (0.1 mmol) and PCyPh2 (0.2 mmol) were used.
reaction is slower with increasing size of the alkyl substituent.
When the isopropyl-substituted substrate 1j was used, desired
product 4jaa was obtained in 40% yield at 70 °C for 24 h. In all
cases, high levels of (Z)-stereo- and diastereoselectivity were
observed.
To further investigate the scope of the present process, tri-n-
alkylboranes were surveyed under the optimized reaction
conditions; Tri-n-hexylborane and triphenethylborane prepared
from 1-hexene and styrene with BH3·SMe2 nicely participated in
Table 4. Reaction with Various Triorganoboranesa
OH
Ph
Pd(OAc)2 (10 mol%)
PCyPh2 (20 mol%)
Ar
+
R
4
OH
(R)3B
+ PhCHO +
Ar
B(pin)
THF, 50 °C
OH
1
2a
3
Based on the results described above, a preliminary reaction
mechanism is proposed in Scheme 3. First, triorganoborane may
coordinate to the oxygen atom of 1 to help it undergo oxidative
addition to Pd(0), which then leads to the formation of η3-
allylpalladium intermediate A. The allylboronate in the allylic
gem-palladium/boryl intermediate A′15 (depicted in another η1-
allyl form for simplicity) undergoes nucleophilic allylation of an
Ph
Ar
5
OH
Ar
OH
OH
Ph
Ph
Ph
Ph
Ph n-Hex
4aab
(53%, dr >99:1)b
Ph n-Bu
4aad
4cac
aldehyde via
a closed transition state B to form (Z)-
(Ar = p-MeO2CC6H4, 55%, dr >99:1) (55%, dr >99:1)
4/5 = 7.8/1 4/5 = 10/1
vinylpalladium intermediate C. In the transition state B,
palladium complex predominantly locates at the axial position
due to gauche strain of the palladium complex with pinacol ester
4/5 = >15/1

4
Tetrahedron
over A1,3 strain. Transmetalation of C with a triorganoborane
3.
(a) Zanoni, G.; Pontiroli, A.; Marchetti, A.; Vidari, G. Eur. J. Org.
Chem. 2007, 3599–3611; (b) Yus, M.; González-Gómez, J. C.;
Foubelo, F. Chem. Rev. 2011, 111, 7774–7854.
(a) Zhu, S.-F.; Yang, Y.; Wang, L.-X.; Zhou, Q.-L. Org. Lett.
2005, 7, 2333–2335; (b) Qiao, X.-C.; Zhu, S.-F.; Zhou, Q.-L.
Tetrahedron Asymmetry 2009, 20, 1254–1261; (c) Qiao, X.-C.;
Zhu, S.-F.; Chen, W.-Q.; Zhou, Q.-L. Tetrahedron Asymmetry
2010, 21, 1216–1220.
(a) Tamaru, Y. J. Organomet. Chem. 1999, 576, 215–231; (b)
Tamaru, Y. Eur. J. Org. Chem. 2005, 2647–2656.
Mita, T.; Higuchi, Y.; Sato, Y. Chem. Eur. J. 2015, 21, 16391–
16394.
Trost, B. M. Angew. Chem. Int. Ed. 1995, 34, 259–281.
Horino, Y.; Aimono, A.; Abe, H. Org. Lett. 2015, 17, 2824–2827.
Wender, P. A.; Verma, V. A.; Paxton, T. J.; Pillow, T. H. Acc.
Chem. Res. 2008, 41, 40−49.
followed by reductive elimination from
a vinylpalladium
intermediate D gives the desired product 4.16, 17
4.
OH
OH
R1
1
B(pin)
R2
B(R3)3
R1 R3
OB(pin)
4
PdLn(0)
5.
6.
R1
R1
B(pin)
PdLn
B(pin)
R2
7.
8.
9.
R1 PdLn
R3
PdLn
O
O
D
H
H
B(R3)3
B(R3)3
A'
A
(R3)2BOH
10. For selected examples of catalytic conditions, see; (a) Tamaru, Y.;
Tanaka, A.; Yasui, K.; Goto, S.; Tanaka, S. Angew. Chem. Int. Ed.
1995, 34, 787–789. (b) Kimura, M.; Shimizu, M.; Tanaka, S.;
Tamaru, Y. Tetrahedron 2005, 61, 3709–3718.
R2CHO
OB(pin)
11. For selected examples of non-catalytic conditions, see; (a)
Hoffmann, R. W. Pure Appl. Chem. 1988, 60, 123–130; (b)
Andersen, M. W.; Hildebrandt, B.; Kosher, G.; Hoffmann, R. W.
Chem. Ber. 1989, 122, 1777–1782; (c) Pietruszka, J.; Schöne, N.
Eur. J. Org. Chem. 2004, 5011–5019; (d) Fang, G. Y.; Aggarwal,
V. K. Angew. Chem. Int. Ed. 2007, 46, 359–362; (e) Possémé, F.;
Deligny, M.; Carreaux, F.; Carboni, B. J. Org. Chem. 2007, 72,
984–989; (f) Berrée, F.; Gernigon, N.; Hercouet, A.; Lin, C. H.;
Carboni, B. Eur. J. Org. Chem. 2009, 329–333; (g) Schmidtmann,
E. S.; Oestreich, M. Angew. Chem. Int. Ed. 2009, 48, 4634–4638;
(h) Chen, M.; Roush, W. R. Org. Lett. 2010, 12, 2706–2709; (i)
Althaus, M.; Mahmood, A.; Suarez, J. R.; Thomas, S. P.;
Aggarwal, V. K. J. Am. Chem. Soc. 2010, 132, 4025–4028; (j)
Che, J. L.-Y.; Scott, H. K.; Hesse, M. J.; Willis, C. L.; Aggarwal,
V. K. J. Am. Chem. Soc. 2013, 135, 5316–5319; (k) Yamamoto,
E.; Takenouchi, Y.; Ozaki, T.; Miya, T.; Ito, H. J. Am. Chem. Soc.
2014, 136, 16515–16521; (l) Gao, X.; Hall, D.; Deligny, M.;
Favre, A.; Carreaux, F.; Carboni, B. Chem. Eur. J. 2006, 12,
3132–3142.
R2
O
H
R1 PdLn
B
O
H
R1
O
H
O
C
B(R3)3
R2
Pd
Ln
O
B(R3)3
B
Scheme 3. A plausible reaction mechanism
In summary, we have developed a palladium-catalyzed three-
component reaction that provides access to a wide variety of (Z)-
anti-homoallylic alcohols starting from easily accessible and
stable 3-(pinacolatoboryl)allyl alcohols, aldehydes, and
triorganoboranes. Both the stereochemistry of the alkene and
diastereoselectivity associated with the catalysis are well
controlled.
12. For selected examples of α-substituted allylboronates, see: (a)
Andersen, M.; Hildebrandt, B.; Koester, G.; Hoffmann, R. W.
Chem. Ber. 1989, 122, 1777–1782; (b) Hoffmann, R. W.; Wolff, J.
J. Chem. Ber. 1991, 124, 563–569; (c) Hall, D. G. Synlett 2007,
1644–1655; (d) Beckmann, E.; Desai, V.; Hoppe, D. Synlett 2004,
2275–2280; (e) Carosi, L.; Lachance, H.; Hall, D. G. Tetrahedron
Lett. 2005, 46, 8981–8985; (f) Ito, H.; Ito, S.; Sasaki, Y.;
Matsuura, K.; Sawamura, M. J. Am. Chem. Soc. 2007, 129,
14856–14857; (g) Peng, F.; Hall, D. G. Tetrahedron Lett. 2007,
48, 3305–3309; (h) Peng, F.; Hall, D. G. J. Am. Chem. Soc. 2007,
129, 3070–3071; (i) Carosi, L.; Hall, D. G. Angew. Chem. Int. Ed.
2007, 46, 5913–5915; (j) Pietruszka, J.; Schone, N.; Frey, W.;
Grundl, L. Chem. Eur. J. 2008, 14, 5178–5197.
Acknowledgments
We thank Prof. Ryuta Miyatake (University of Toyama) for his
assistance with HRMS measurements. This work was financially
supported by the JSPS KAKENHI Grant Number 15K05496.
References and notes
1.
σ-Allylpalladium-mediated nucleophilic allylation reactions, see:
(a) Kurosawa, H.; Urabe, A. Chem. Lett. 1985, 1839–1840; (b)
Kurosawa, H.; Ogoshi, S. Bull. Chem. Soc. Jpn. 1998, 71, 973–
981; (c) Nakamura, H.; Iwama, H.; Yamamoto, Y. J. Am. Chem.
Soc. 1996, 118, 6641–6647; (d) Nakamura, H.; Nakamura, K.;
Yamamoto, Y. J. Am. Chem. Soc. 1998, 120, 4242–4243; (e)
Fernandes, R. A.; Stimac, A.; Yamamoto, Y. J. Am. Chem. Soc.
2003, 125, 14133–14139; (f) Soiln, N.; Kjellgre, J.; Szabó, K. J.
Angew. Chem. 2003, 115, 3784–3786; Angew. Chem. Int. Ed.
2003, 42, 3656–3658; (g) Solin, N.; Kjellgren, J.; Szabó, K. J. J.
Am. Chem. Soc. 2004, 126, 7026–7033; (h) Barczak, N. T.; Grote,
R. E.; Jarvo, E. R. Organometallics 2007, 26, 4863–4865; (i)
Shaghafi, M. B.; Kohn, B. L.; Jarvo, E. R. Org. Lett. 2008, 10,
4743–4746.
13.
A
single synthetic-step operation to synthesize homoallylic
alcohols through conversion to allylboron reagents via tandem
hydroboration of alkynes−isomerization of (E)-1-
alkenylboronates, see: (a) Miura, T.; Nishida, Y.; Morimoto, M.;
Murakami, M. J. Am. Chem. Soc. 2013, 135, 11497–11500; (b)
Miura, M.; Nishida, Y.; Murakami, M. J. Am. Chem. Soc. 2014,
136, 6223–6226.
14. (a) P. B. Mackenzie, J. Whelan, B. Bosnich, J. Am. Chem. Soc.
1985, 107, 2046-2054; (b) H. Kurosawa, S. Ogoshi, N. Chatani,
Y. Kawasaki, S. Murai, I. Ikeda, Chem. Lett. 1990, 1745-1748; (c
.- . ckvall, K. L. Granberg, A. Heumann, Isr. J. Chem. 1991,
31, 17-24; (d . . ranberg, .- . ckvall, J. Am. Chem. Soc.
1992, 114, 6858-6863; (e) C. Amatore, S. Gamez, A. Jutand, G.
Meyer, M. Moreno-Ma as, L. Morral, R. Pleixats, Chem. Eur. J.
2000, 6, 3372-3376; (f) C. Amatore, A. Jutand, L. Mensah, G.
Meyer, J.-C. Fiaud, J. Y. Legros, Eur. J. Org. Chem. 2006, 1185-
1192; (g) G. Blessley, P. Holden, M. Walker, J. M. Brown, V.
Gouverneur, Org. Lett. 2012, 14, 2754-2757; (h) H. L. Amanda, J.
P. Morken, Org. Lett. 2014, 16, 2096-2099.
15. Intramolecular protonation of the boronate oxygen by the
Brønsted-acid hydroxyl group on palladium might preferentially
lead to the formation of A’. In addition, it would increase boron’s
electrophilicity. For related examples, see: (a) Jain, P.; Antilla, J.
C. J. Am. Chem. Soc. 2010, 132, 11884–11886 and ref 12e.
16. The transmetallation step is not clear at the moment.
2.
Recent studies on σ-allylpalladium-mediated enantioselective
carbonyl allylation reactions, see: (a) Zanoni, G.; Gladiali, S.;
Marchetti, A.; Piccinini, P.; Tredici, I.; Vidari, G. Angew. Chem.
2004, 116, 864–867; Angew. Chem. Int. Ed. 2004, 43, 846–849;
(b) Howell, G. P.; Minnaard, A. J.; Ferigna, B. L. Org. Biomol.
Chem. 2006, 4, 1278–1283; (c) Onomura, O.; Fujimura, N.; Oda,
T.; Matsumura, Y.; Demizu, Y. Heterocycles 2008, 76, 177–182;
(d) Wang, W.; Zhang, T.; Shi, M. Organometallics 2009, 28,
2640–2642; (e) Jiang, J.-J.; Wang, D.; Wang, W.-F.; Yuan, Z.-L.;
Zhao, M.-X.; Wang, F.-J.; Shi, M. Tetrahedron Asymmetry 2010,
21, 2050–2054; (f) Zhu, S.-F.; Qiao, X.-Q.; Zhang, Y.-Z.; Wang,
L.-X.; Zhou, Q.-L. Chem. Sci. 2011, 2, 1135–1140; (g) Yus, M.;
González-Gómez, J. C.; Foubelo, F. Chem. Rev. 2011, 111, 7774–
7854. (h) Tsukamoto, H.; Kawase, A.; Doi, T. Chem. Commun.
2015,51,8027–8030.
17. Another possible reaction path based on Zhou’s observations
might be considered, see; ref 2.

5
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Supplementary Material
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Supplementary material that may be helpful in the review process
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6
Tetrahedron
Highlights
Allylic alcohols can be utilized directly as an allylating agent.
(Z)-anti-Homoallylic alcohols can be readily synthesized.
Triorganoboranes are used as a coupling reagent.
Pd/R3B induces the formation of π-allylpalladium species from allylic alcohols.