(2-Fluoroallyl)boronates: New reagents for diastereoselective 2-fluoroallylboration of aldehydes

Article abstract of DOI:10.1039/c8ob01103f

A Pd-catalyzed borylation of 2-fluoroallyl chlorides with B₂pin₂ in the presence of [(2-MeAll)PdCl]₂/TMEDA or [(2-MeAll)Pd(IPr)Cl] was developed to afford (2-fluoroallyl)pinacolboronates with high Z-selectivity. The products proved to be useful for anti-selective 2-fluoroallylboration of aromatic and aliphatic aldehydes.

Full text of DOI:10.1039/c8ob01103f

View Article Online
View Journal
Organic &
Biomolecular
Chemistry
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: M. A. Novikov and
O. M. Nefedov, Org. Biomol. Chem., 2018, DOI: 10.1039/C8OB01103F.
This is an Accepted Manuscript, which has been through the
Volume 14 Number
1 7 January 2016 Pages 1–372
Royal Society of Chemistry peer review process and has been
accepted for publication.
Organic &
Biomolecular
Chemistry
www.rsc.org/obc
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
author guidelines.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the ethical guidelines, outlined
in our author and reviewer resource centre, still apply. In no
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
ISSN 1477-0520
COMMUNICATION
Takeharu Haino et al.
Solvent-induced emission of organogels based on tris(phenylisoxazolyl)
benzene
rsc.li/obc

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 1 of 6
View Article Online
DOI: 10.1039/C8OB01103F
Journal Name
COMMUNICATION
(2-Fluoroallyl)boronates: new reagents for diastereoselective 2-
fluoroallylboration of aldehydes
Received 00th January 20xx,
Accepted 00th January 20xx
Maxim A. Novikov*, and Oleg M. Nefedov
DOI: 10.1039/x0xx00000x
www.rsc.org/
A Pd-catalyzed borylation of 2-fluoroallyl chlorides with B2pin2 in enantioselective 2-fluoroallylation of aldehydes or primary
the presence of [(2-MeAll)PdCl]2/TMEDA or [(2-MeAll)Pd(IPr)Cl] alcohols with 3-chloro-2-fluoropropene using alcohols as
was developed to afford (2-fluoroallyl)pinacolboronates with high stoichiometric reductants has also been described (Scheme
Z-selectivity. The products proved to be useful for anti-selective 2- 1b).2e To the best of our knowledge, (2-fluoro-3-
fluoroallylboration of aromatic and aliphatic aldehydes.
phenylallyl)trimethylsilane is the only example of 2-fluoroallyl
silane, recently obtained by high-temperature Pd-catalyzed
silylation of 2-fluorocinnamic acetate with Me3SiSiMe3
(Scheme 1c) and used for Lewis acid-mediated syn-selective
allylation of aldehydes.2f
Fluorinated molecules have attracted great attention in
modern medicinal chemistry for drug discovery and
development, as molecular probes in 19F NMR imaging of
biological systems, and in [18F]-positron emission tomography.1
Such broad applications derive from the unique combination
of small atomic radius, high electronegativity, and low
polarizability of the fluorine atom, which results in a significant
increase in metabolic stability, lipophilicity, membrane
permeability, and binding affinity for target molecules.
Known methods:
CrCl2
or In0
OH
F
F
O
(a)
[2a-d]
R
X
+
R'
R''
R'
O
R''
R
Y
Y
In particular, fluorinated allylic nucleophiles2-5 are
(b)
(c)
F
OH
OH
F
[Ir]*
+
Cl
[2e]
[2f]
R'
promising building blocks for the diastereo- and
R'
R'
R'
O
enantioselective
construction
of
α/β-substituted
F
F
F
OH
F
F
Me3SiSiMe3
fluoroalkenes,6,7 which have various biological activities such
as anticancer,8 antimicrobial,9 anti-HIV,10 and antidiabetic
effects.11 Moreover, monofluoroalkenes serve as bioisosteres
of amide bonds.12
Ph
SiMe3
OAc
R'
Pd(PPh3)4
160°C
TICl4
Ph
Ph
Current work:
B2pin2
O
F
[(2-MeAll)PdCl] 2
TMEDA
Cl
OH
We have recently disclosed a copper(I)-catalyzed ring-
opening reaction of gem-chlorofluoro- and gem-
bromofluorocyclopropanes for the efficient synthesis of 2-
fluoroallyl halides13a,b and O-13c and N-derivatives,13d which
have been used as electrophiles in C-C bond-forming reactions
with cuprates14 and palladium-catalyzed allylation of
enolates.15
R
Bpin
R
R'
R
R'
DCE
60°C
R
R
R
Scheme 1. Umpolung reactivity of 2-fluoroallyl halides/pseudohalides
Herein, we report a mild method for the umpolung of 2-
fluoroallyl chlorides by converting them into (2-
fluoroallyl)pinacolboronates via [Pd0]-catalyzed borylation with
B2pin2.
However, only few examples of umpolung of 2-fluoroallyl
halides serving as 2-fluoroallyl nucleophiles are known.2
Namely, a low-valent metal reduction of 2-fluoroallyl chlorides
and bromides with In0 or CrCl2 in the presence of aldehydes or
ketones has been reported (Scheme 1a).2a-d Iridium-catalyzed
At the outset, the conversion of 2-fluoroallyl halides into
the corresponding 2-fluoroallyl silanes or boronates was
investigated under different conditions using 2-fluorocinnamyl
chloride Z-1a (Z/E > 99.9) as a model substrate (Table 1).
Silylation of 1a with TMSCl in the presence of Mg turnings
gave the target silane Z-2a in only moderate yield along with
phenylallene as the major byproduct formed by fluoride
elimination from the intermediate 2-fluoroallyl magnesium
chloride (entry 1). Moreover, small amounts of other isomers
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 2 of 6
View Article Online
DOI: 10.1039/C8OB01103F
COMMUNICATION
Journal Name
of 2a, i.e., E-2a and 2’a, were detected. Nevertheless, the and 1’a) was carried out; notably, in all cases, the (Z)-isomer of
practical advantages of this approach for the preparation of Z- boronate 3a (Scheme 2) was obtained almost exclusively.
2a, namely, the use of inexpensive reagents and easy scale up
(entry 2), encouraged further investigations.
The reaction with more sterically hindered TBSCl as the
electrophile resulted in complete elimination of fluorine and
no detection of 2-fluoroallyl silane (entry 4). Borylation of 1a
with HBpin16 under the same reaction conditions gave 2-
fluorocinnamyl boronate 3a in low yield as a mixture of Z/E
isomers (entry 5).
Table 1. Silylation and borylation of 2-fluoro-3-phenylallyl chloride 1a (selected
examples, see ESI for details)
Scheme 2. Borylation of different isomers of 1a and 1’a
Next, we found that purification by column
Yield, (%)a
chromatography on silica gel provided boronate 3a only in
M
Reaction conditions
2/3
Z/E
2’/3’
3
moderate yield (Table 1, entry 6). Moreover, upon storage at
room temperature for several hours or overnight in a freezer
(–18 °C), 3a readily decomposed to a complex mixture of
products. Nevertheless, 3a could be used in a one-pot
allylboration of aromatic aldehydes to form anti-3-
fluorohomoallylic alcohols in moderate to good yields with
high anti-selectivity17 (Table 2, entries 1–6). Because of their
lower reactivity, the allylboration of aliphatic aldehydes
required the addition of catalytic Sc(OTf)3 (entries 7, 8).18
With the optimized conditions in hand, the substrate scope
was investigated with various substituted 2-fluoroallyl
chlorides 1a-1i prepared by CuCl-catalyzed isomerization of
the corresponding gem-chlorofluorocyclopropanes according
to a previously reported procedure13b (Table 2, see ESI for
details). In general, borylation of alkyl-substituted 2-fluoroallyl
chlorides required longer reaction times (18–24 h vs. 3–5 h)
and was less efficient than that of aryl-substituted derivatives
(entries 12–19). Nevertheless, allylboration of aromatic
aldehydes still proceeded with high diastereoselectivity.
1
2
3
SiMe3
SiMe3
SiMe3
Mg, Me3SiCl, THF, 25 °С, 5 h
58
97/3
—//—, 100 mmol scale
Me3SiSiMe3, Pd(OAc)2, DCE,
80 °C, 4 h
(45) (99/1)
—
64
84/16
18
4
5
TBS
Mg, TBSCl, THF, 25 °C, 3 h
Mg, HB(pin), THF, 25 °С, 3 h
0
—
0
0
Bpin
30
99
92/8
98/2
B2(pin)2, [(2-MeAll)PdCl]2
,
6
7
Bpin
Bpin
0
0
TMEDA, DCE, 60 °C, 3 h
B2(pin)2, [(2-MeAll)Pd(IPr)Cl],
DCE, 60 °C, 10 h
(74) (96/4)
100 98/2
a 19F NMR yields; isolated yields and Z/E are in parenthesis.
Pd-catalyzed silylation of 1a with Me3SiSiMe3 in the
presence of Pd(OAc)2 proceeded with low regio- and
stereoselectivity. Phosphine and diamine ligands significantly
reduced the reaction rate but only slightly affected the
selectivity (entry 3; see ESI for details).
To our delight, Pd-catalyzed Miyaura borylation of 1a with
B2pin2 provided the desired 2-fluorocinnamyl boronate 3a in
nearly quantitative yield. Precatalyst screening showed that
[(2-MeAll)PdCl]2/TMEDA and [(2-MeAll)Pd(IPr)Cl] in DCE were
the most active (entries 6, 7; see ESI for detailed ligand
Remarkably, the reactions of regioisomeric mixtures of 2-
fluoroallyl chlorides were also successful. Namely, borylation
of a mixture of 1h and 1’h or 1i and 1’i gave nearly isomerically
pure (Z)-boronates 3h or 3i, respectively (entries 18, 19).
A major problem associated with the use of the Bpin group
screening),
diastereoselectivity (Z/E
regioisomer 3’a
affording
3a
with
high
regio-
and
is the low Z/E-selectivity of the reaction of
α-substituted
=
98/2) without formation of
boronates.19 In fact, the reaction of 1,3-dimethyl-substituted
boronate 3g with 4-nitrobenzaldehyde gave anti-alcohol 5gb
as a mixture of Z/E-isomers (entry 16). Fortunately, this issue
was easily overcome by adding 20 mol % BF3·Et2O (entries 15,
17).20
.
The reaction mechanism presumably involves oxidative
addition of [Pd0] to 1a to give a 2-fluoroallyl palladium
complex, followed by transmetalation and reductive
elimination. To confirm the formation of the allyl palladium
complex, borylation of all three isomers of 1a (i.e., Z-1a, E-1a
,
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 3 of 6
View Article Online
DOI: 10.1039/C8OB01103F
Journal Name
COMMUNICATION
Table 2. Substrate scope
Entry
2-Fluoroallyl chloride a
2-Fluoroallyl boronate b
3-Fluorohomoallyl alcohol c
1
2
3
4
5
6
7
8
1a (98%, Z/E 88/12)
3a (99%, Z/E 98/2)
R = C6H5-: 5aa (75%, d.r. 96/4)
R = (4-NO2)C6H4-: 5ab (87%, d.r. > 20/1)
R = (4-MeO)C6H4-: 5ac (92%, d.r. 98/2) d
R = (3-MeO)C6H4-: 5ad (89%, d.r. 99/1)
R = 3-Pyridyl: 5ae: 88% (d.r. 97/3)
R = Ph-CH=CH-: 5af: 70% (d.r. 93/7)
R = n-heptyl-: 5ag (74%, d.r. 96/4) (10 mol % Sc(OTf)3) e
R = (CH3)2CHCH2-: 5ah (54%, d.r. 98/2) (10 mol % Sc(OTf)3) e
9
R = 4-F: 1b (97%, Z/E 79/21)
R = 4-NO2: 1c (93%, Z/E 87/13)
R = 2-NO2: 1d (85%, Z/E 86/14)
R = 4-F: 3b (97%, Z/E 98/2)
R = 4-NO2: 3c (100%, Z/E 98/2)
R = 2-NO2: 3d (99%, Z/E 97/3)
R = 4-F: 5ba (78%, d.r. >20/1)
R = 4-NO2: 5ca (71%, d.r. >20/1)
R = 2-NO2: 5da (51%, d.r. >20/1)
10
11
1e (93%)
1f (62%)
3e (76%)
3f (80%)
5eb (69%, d.r. > 20/1)
12
13
14
R = H: 5fa (53%)
R = NO2: 5fb (61%)
R = H: 5ga (57%, d.r. > 20/1, Z/E > 20/1) (20 mol % BF3·Et2O) f,g
R = NO2: 5gb (68%, d.r. > 20/1, Z/E 39/61)
R = NO2: 5gb (74%, d.r. > 20/1, Z/E 98/2) (20 mol % BF3·Et2O) f,g
1g (89%, Z/E 92/8)
3g (88%, Z/E > 20/1)
15
16
17
1h, 1’h (92%, Z/E/1’ 47/37/16)
5ha (68%, d.r. 96/4)
18
3h (98%, Z/E 97/3)
1i, 1’i (84%, Z/E/1’ 64/23/13)
5ia (65%, d.r. 97/3)
19
3i (88%, Z/E 95/5)
General procedure: 2-Fluoroallyl chloride (0.50 mmol), B2pin2 (0.525 mmol), [(2-MeAll)PdCl]2 (0.0125 mmol), and TMEDA (0.025 mmol) in DCE (1.0 mL) were
heated at 60 °C for 3–24 h. After completion of the borylation step, 0.60 mmol of aldehyde were added at r.t., and the mixture was stirred for 1–3 days.
a
Isolated yields (see ESI for details); b 19F NMR yields (see ESI for details); c Isolated yields and d.r. (no changes in d.r. were observed during chromatographic
purification); d 2.0 equiv. of NaOAc were added prior to the addition of anisaldehyde in order to convert ClBpin (a stoichiometric byproduct of the borylation)
into AcOBpin. Otherwise, substantial substitution of -OH on -Cl in 5ac occurred (see ESI); e 20 h at r.t.; f 5 h at –30 °C; g MS4Å were added.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 4 of 6
View Article Online
DOI: 10.1039/C8OB01103F
Journal Name
COMMUNICATION
Ramachandran, A. Tafelska-Kaczmarek and A. Chatterjee, J. Org.
Chem., 2012, 77, 9329–9333; (d) B. Zhang and X. Zhang, Chin. J.
Chem., 2016, 34, 477–480; (e) X. Yang, Z.-H. Cao, Y. Zhou, F.
Cheng, Z.-W. Lin, Z. Ou, Y. Yuan and Y.-Y. Huang, Org. Lett., 2018,
20, 2585–2589; (f) D. Seyferth, R. M. Simon, D. J. Sepelak and H.
A. Klein, J. Am. Chem. Soc., 1983, 105, 4634–4639; (g) T. Ishihara,
S. Miwatashi, M. Kuroboshi and K. Utimoto, Tetrahedron Lett.,
1991, 32, 1069–1072; (h) Z. Y. Yang and D. J. Burton, J. Org.
Chem., 1991, 56, 1037–1041; (i) M. Rajaonah, M. H. Rock, J.-P.
Bégué, D. Bonnet-Delpon, S. Condon and J.-Y. Nédélec,
Tetrahedron Lett., 1998, 39, 3137–3140; (j) M. Kirihara, T.
Takuwa, S. Takizawa, T. Momose and H. Nemoto, Tetrahedron,
2000, 56, 8275–8280; (k) W. Peng, P. He, S. Zhu and Z. Li,
Tetrahedron Lett., 2004, 45, 3677–3680; (l) W. Peng, J. Zhao and
S. Zhu, J. Fluor. Chem., 2006, 127, 360–366.
Conclusions
A
new method for the preparation of (2-
fluoroallyl)pinacolboronates was developed involving CuCl-
catalyzed isomerization of readily available gem-
chlorofluorocyclopropanes
to
stereoisomeric
(or
regioisomeric) mixtures of 2-fluoroallyl chlorides, followed by
Pd-catalyzed borylation with B2pin2 in the presence of [(2-
MeAll)PdCl]2/TMEDA or [(2-MeAll)Pd(IPr)Cl]. Various (2-
fluoroallyl)pinacolboronates were obtained with high Z-
selectivity, which were shown to be useful for anti-selective 2-
fluoroallylboration of aromatic and aliphatic aldehydes.
4 For 3,3-difluoroallylic nucleophiles, see: T. Kumar, F. Massicot, D.
Harakat, S. Chevreux, A. Martinez, K. Bordolinska, P.
Preethalayam, R. Kokkuvayil Vasu, J.-B. Behr, J.-L. Vasse and F.
Jaroschik, Chem. Eur. J., 2017, 23, 16460–16465.
Conflicts of interest
There are no conflicts of interest to declare.
5 For 3-fluoroallylic nucleophiles, see: A. Macé, F. Tripoteau, Q.
Zhao, E. Gayon, E. Vrancken, J.-M. Campagne and B. Carboni, Org.
Lett., 2013, 15, 906–909.
6 For reviews, see: (a) J. M. Percy, Top. Curr. Chem., 1997, 193,
131–195; (b) G. Landelle, M. Bergeron, M.-O. Turcotte-Savard and
J.-F. Paquin, Chem. Soc. Rev., 2011, 40, 2867–2908; (c) H. Yanai
and T. Taguchi, Eur. J. Org. Chem., 2011, 2011, 5939–5954; (d) A.
S. Konev and A. F. Khlebnikov, Collect. Czech. Chem. Commun.,
2008, 73, 1553–1611.
Acknowledgements
This work was funded by the Russian Federation President
Council for Grants (grant no. MK-390.2018.3). The authors
greatly thank Dr. Roman A. Novikov from ZIOC RAS for 1D and
2D NMR assistance.
7 For the most recent advances in functionalized fluoroalkene
synthesis, see: (a) L. Yang, W.-W. Ji, E. Lin, J.-L. Li, W.-X. Fan, Q. Li
and H. Wang, Org. Lett., 2018, 20, 1924–1927; (b) X. Lu, Y. Wang,
B. Zhang, J.-J. Pi, X.-X. Wang, T.-J. Gong, B. Xiao and Y. Fu, J. Am.
Chem. Soc., 2017, 139, 12632–12637; (c) J. Li, Q. Lefebvre, H.
Yang, Y. Zhao and H. Fu, Chem. Commun., 2017, 53, 10299–
10302; (d) S. B. Lang, R. J. Wiles, C. B. Kelly and G. A. Molander,
Angew. Chem. Int. Ed., 2017, 56, 15073–15077; (e) C. D. McCune,
M. L. Beio, J. M. Sturdivant, R. de la Salud-Bea, B. M. Darnell and
D. B. Berkowitz, J. Am. Chem. Soc., 2017, 139, 14077–14089; (f) H.
Sommer and A. Fürstner, Chem. Eur. J., 2017, 23, 558–562; (g) J.
Xie, J. Yu, M. Rudolph, F. Rominger and A. S. K. Hashmi, Angew.
Chem. Int. Ed., 2016, 55, 9416–9421.
8 (a) S. Osada, S. Sano, M. Ueyama, Y. Chuman, H. Kodama and K.
Sakaguchi, Bioorg. Med. Chem., 2010, 18, 605–611; (b) J.
Kanazawa, T. Takahashi, S. Akinaga, T. Tamaoki and M. Okabe,
Anti-Cancer Drugs, 1998, 9, 653–657.
9 (a) R. J. Sciotti, M. Pliushchev, P. E. Wiedeman, D. Balli, R. Flamm,
A. M. Nilius, K. Marsh, D. Stolarik, R. Jolly, R. Ulrich and S. W.
Djuric, Bioorg. Med. Chem. Lett., 2002, 12, 2121–2123; (b) Y.
Asahina, K. Iwase, F. Iinuma, M. Hosaka and T. Ishizaki, J. Med.
Chem., 2005, 48, 3194–3202.
Notes and references
1 (a) P. Kirsch, Modern Fluoroorganic Chemistry: Synthesis,
Reactivity, Applications, Wiley-VCH Verlag GmbH & Co. KGaA,
2004; (b) I. Ojima, Ed., Fluorine in Medicinal Chemistry and
Chemical Biology, John Wiley & Sons, Ltd, Chichester, UK, 2009;
(c) W. K. Hagmann, J. Med. Chem., 2008, 51, 4359–4369; (d) E. P.
Gillis, K. J. Eastman, M. D. Hill, D. J. Donnelly and N. A. Meanwell,
J. Med. Chem., 2015, 58, 8315–8359; (e) P. Richardson, Expert
Opin. Drug Discov., 2016, 11, 983–999.
2 Several types of fluoroallylic nucleophiles are known. For 2-
fluoroallylic nucleophiles, see: (a) G. Lemonnier, T. Poisson, S.
Couve-Bonnaire and X. Pannecoucke, Tetrahedron Lett., 2013, 54,
2821–2824; (b) G. Lemonnier, N. Van Hijfte, M. Sebban, T.
Poisson, S. Couve-Bonnaire and X. Pannecoucke, Tetrahedron,
2014, 70, 3123–3133; (c) G. Lemonnier, N. V. Hijfte, T. Poisson, S.
Couve-Bonnaire and X. Pannecoucke, J. Org. Chem., 2014, 79,
2916–2925; (d) R. Baati, V. Gouverneur and C. Mioskowski, J. Org.
Chem., 2000, 65, 1235–1238; (e) A. Hassan, T. P. Montgomery and
M. J. Krische, Chem. Commun., 2012, 48, 4692–4694; (f) T.
Hayashi, Y. Usuki and H. Iio, J. Fluor. Chem., 2010, 131, 709–713.
3 For 1,1-difluoroallylic nucleophiles, see: (a) P. V. Ramachandran,
A. Tafelska-Kaczmarek and K. Sakavuyi, Org. Lett., 2011, 13, 4044–
4047; (b) V. P. Ramachandran, A. Tafelska-Kaczmarek, K. Sakavuyi
and A. Chatterjee, Org. Lett., 2011, 13, 1302–1305; (c) P. V.
10 S. Oishi, H. Kamitani, Y. Kodera, K. Watanabe, K. Kobayashi, T.
Narumi, K. Tomita, H. Ohno, T. Naito, E. Kodama, M. Matsuoka
and N. Fujii, Org. Biomol. Chem., 2009, 7, 2872–2877.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 4
Please do not adjust margins

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 5 of 6
View Article Online
DOI: 10.1039/C8OB01103F
Journal Name
COMMUNICATION
11 (a) S. D. Edmondson, L. Wei, J. Xu, J. Shang, S. Xu, J. Pang, A.
Chaudhary, D. C. Dean, H. He, B. Leiting, K. A. Lyons, R. A. Patel, S.
B. Patel, G. Scapin, J. K. Wu, M. G. Beconi, N. A. Thornberry and A.
E. Weber, Bioorg. Med. Chem. Lett., 2008, 18, 2409–2413; (b) T.
Deng, S. Shan, Z.-B. Li, Z.-W. Wu, C.-Z. Liao, B. Ko, X.-P. Lu, J.
Cheng and Z.-Q. Ning, Biol. Pharm. Bull., 2005, 28, 1192–1196.
12 For reviews, see: (a) A. Choudhary, R. T. Raines, ChemBioChem.,
2011, 12, 1801–1807; (b) J. T. Welch, Fluoroolefin dipeptide
isosteres: structure, syntheses, and applications, in: A. Tressaud,
G. Haufe, Fluorine and Health, Elsevier, Amsterdam, 2008, pp.
699–735.
13 (a) N. V. Volchkov, M. A. Novikov, M. B. Lipkind and O. M.
Nefedov, Mendeleev Commun., 2013, 23, 19–21; (b) M. A.
Novikov, N. V. Volchkov, M. B. Lipkind and O. M. Nefedov, Russ.
Chem. Bull., 2013, 62, 71–82; (c) M. A. Novikov, N. V. Volchkov, M.
B. Lipkind and O. M. Nefedov, J. Fluor. Chem., 2015, 180, 131–
143; (d) M. A. Novikov, Y. A. Ibatov, N. V. Volchkov, M. B. Lipkind,
S. E. Semenov and O. M. Nefedov, J. Fluor. Chem., 2017, 194, 58–
72.
14 T. Nihei, Y. Kubo, T. Ishihara and T. Konno, J. Fluor. Chem., 2014,
167, 110–121.
15 (a) T. Allmendinger, C. Angst and H. Karfunkel, J. Fluor. Chem.,
1995, 72, 247–253; (b) M. Yamamoto, S. Hayashi, K. Isa and M.
Kawatsura, Org. Lett., 2014, 16, 700–703; (c) M. Kawatsura, S.
Wada, S. Hayase and T. Itoh, Synlett, 2006, 2483–2485.
16 J. W. Clary, T. J. Rettenmaier, R. Snelling, W. Bryks, J. Banwell,
W. T. Wipke and B. Singaram, J. Org. Chem., 2011, 76, 9602–9610.
17 Allylboration of aldehydes with trans-allylboronates is well
known to proceed with anti-selectivity imposed by
a six-
membered cyclic transition state, see: H. Lachance and D. G. Hall,
Org. React., 2009, 73, 1–574.
18 Lewis acids are known to promote allylboration of carbonyl
compounds without affecting the diastereoselectivity, see ref. 17
.
19 R. W. Hoffman and U. Weidmann, J. Organomet. Chem., 1980,
195, 137–146.
20 (a) H. Ito, S. Ito, Y. Sasaki, K. Matsuura and M. Sawamura, J. Am.
Chem. Soc., 2007, 129, 14856–14857; (b) F. Peng and D. G. Hall,
Tetrahedron Lett., 2007, 48, 3305–3309; (c) M. Chen and W. R.
Roush, Org. Lett., 2010, 12, 2706–2709.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins

Organic & Biomolecular Chemistry
Page 6 of 6
View Article Online
DOI: 10.1039/C8OB01103F
TOC entry
(2-Fluoroallyl)boronates: new reagents for diastereoselective 2-
fluoroallylboration of aldehydes
Maxim A. Novikov*, and Oleg M. Nefedov
N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp.,
119991 Moscow, Russian Federation
Fax: +7499 135 63 90; e-mail: manovikov@ioc.ac.ru
New reagents for anti-selective 2-fluoroallylboration of aromatic and aliphatic aldehydes —
(2-fluoroallyl)pinacolboranes, were prepared by Pd-catalyzed borylation of 2-fluoroallyl
chlorides.