Alkylboronic esters from palladium- and nickel-catalyzed borylation of primary and secondary alkyl bromides

Article abstract of DOI:10.1002/adsc.201200136

Palladium- and nickel-catalyzed cross-coupling recations of unactivated alkyl bromides with diboron reagents have been developed as practical methods for the synthesis of primary and secondary alkylboronic esters. These reactions extend the concept and utility of Pd- and Ni-catalyzed cross-coupling of aliphatic electrophiles. They also show different substrate selectivity and ligand dependence as compared to the recently reported Cu-catalyzed borylation reaction. Copyright

Full text of DOI:10.1002/adsc.201200136

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DOI: 10.1002/adsc.201200136
Alkylboronic Esters from Palladium- and Nickel-Catalyzed
Borylation of Primary and Secondary Alkyl Bromides
Jun Yi,a,b Jin-Hui Liu,a Jun Liang,c Jian-Jun Dai,a Chu-Ting Yang,a,c Yao Fu,a
and Lei Liua,b,c,
*
a
Joint Laboratory of Green Synthetic Chemistry, Department of Chemistry, University of Science and Technology of
China, Hefei 230026, Peopleꢀs Republic of China
E-mail: lliu@mail.tsinghua.edu.cn
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of
Sciences, Shanghai 200032; Peopleꢀs Republic of China
b
c
Department of Chemistry, Tsinghua University, Beijing 100084, Peopleꢀs Republic of China
Received: February 17, 2012; Published online: May 30, 2012
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201200136.
Abstract: Palladium- and nickel-catalyzed cross-
coupling recations of unactivated alkyl bromides
with diboron reagents have been developed as prac-
tical methods for the synthesis of primary and sec-
ondary alkylboronic esters. These reactions extend
the concept and utility of Pd- and Ni-catalyzed
cross-coupling of aliphatic electrophiles. They also
show different substrate selectivity and ligand de-
pendence as compared to the recently reported Cu-
catalyzed borylation reaction.
lyzed olefin hydroboration,[7] Ru-, Rh-, Ir-, and Re-
catalyzed alkane C H borylation, and Pd-, Ni-, Fe-,
[8]
À
and Cu-catalyzed b-borylation of unsaturated carbon-
yl compounds.[9] Very recently, we developed a new
approach for the synthesis of alkylboronic acid deriv-
atives through Cu-catalyzed borylation of alkyl hal-
ides and pseudohalides.[10] In the present work we
wish to report that Pd and Ni catalysts can also pro-
mote the borylation of alkyl bromides with diboron
reagents.[11] Note that intensive studies have been car-
ried out recently to develop Pd- and Ni-catalyzed
cross-coupling of aliphatic electrophiles with a variety
of carbon nucleophiles.[12,13] Conceptually the present
work extends this category of reactions to the use of
boron nucleophiles.
Keywords: alkyl halides; cross-coupling; nickel; or-
ganoboron compounds; palladium
Our study began with the borylation of 1a by
B2pin2 (Table 1). When PdACHTNUTRGENNUG(OAc)2/PPh3 or PdACHTUNGTERN(NUGN OAc)2/
Alkylboronic acids are interesting compounds in me- PCy3 was used as the catalyst, we observed low yields
dicinal chemistry. Some of them have been found to of the desired product (entries 1 and 2). Subsequently
inhibit enzymes including arginase, histone deacety- we tested different solvents (entries 3 and 4) and li-
lase, and fatty acid amide hydrolase.[1] A particular al- gands (entries 5–7), yet the yield remained barely im-
kylboronic acid (bortezomib) is already an approved proved. A breakthrough was then made when the
drug for treating relapsed multiple myeloma and ligand was changed to PACTHNUTRGNEUNG(t-Bu)2Me·HBF4 (entry 8).
mantle cell lymphoma.[2] In synthetic chemistry alkyl- This ligand was previously used by Fu et al. for Pd-
boronic acid derivatives are often employed as re- catalyzed cross-coupling of alkyl halides with organo-
agents for transition metal-catalyzed cross-coupling boronic acids and arylsilanes.[12] After the catalyst was
reactions of CACHTUNGTRENNUNG 2ACHTUTGNREN(NNGU dba)3, the yield increased to 45%
(sp3) organometallics.[3,4] Moreover, changed to Pd
chiral alkylboronic acid derivatives can be used as (entry 9). Further optimization of the base revealed
configurationally stable organometallic reagents for that NaOMe afforded the highest yield (84%,
À
À
À
making C N, C O, and C C bonds with stereocon- entry 10). Note that when Pd
2ACHTUNGTREN(NNUG dba)3 was replaced by
trol.[5]
3 mol% CuI in the optimized conditions, 3a was ob-
To prepare alkylboronic acid derivatives, classical tained in only 20% yield (entry 11). Thus the Pd-cata-
methods rely on the reaction of alkyl-Li or alkyl-Mg lyzed borylation reaction is not due to Cu contamina-
reagents with suitable boron compounds.[6] More tion. Furthermore, in a control experiment we con-
recent efforts in this field are directed to transition firmed that the reaction does not take place without
metal-catalyzed methods, including Rh- and Ir-cata- Pd (entry 12).
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Table 1. Pd-catalyzed borylation of n-hexyl bromide.
Entry
Pd salt (5 mol%)
Pd(OAc)2
Ligand (10 mol%)
Base
Solvent (2 mL)
Yield of 3a [%][a]
1
2
3
4
5
6
7
8
G
L1
L2
L2
L2
L3
L4
L5
L6
L6
L6
L6
L6
KO-t-Bu
KO-t-Bu
KO-t-Bu
KO-t-Bu
KO-t-Bu
KO-t-Bu
KO-t-Bu
KO-t-Bu
KO-t-Bu
NaOMe
NaOMe
NaOMe
DMF
DMF
10
15
16
24
trace
trace
20
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
2A(dba)3
2A(dba)3
R
N
R
N
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
G
tert-amyl alcohol
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
32
45
9[b]
10[b]
11[d]
12[e]
Pd
Pd
U
87 (84)[c]
20
CuI
–
0
[a]
GC yields after 24 h.
1.5 mol% Pd2ACHTUNGTRENNUNG(dba)3, 6 mol% L6, and 3.0 equiv. of base were added.
Isolated yield is shown in the parenthesis.
3 mol% CuI, 6 mol% L6, and 3.0 equiv. of NaOMe were added.
6 mol% L6 and 3.0 equiv. of NaOMe were added.
[b]
[c]
[d]
[e]
Having optimized the conditions, we next examined ferent transformations. The Pd-catalyzed reaction en-
the scope of the Pd-catalyzed borylation reaction ables the selective borylation of a primary alkyl bro-
(Table 2). Our results show that a variety of syntheti- mide and, therefore, provides a complementary utility
cally important functional groups including cyano as compared to the Cu-catalyzed method.
(3b), ester (3e, 3f), ether (3g, 3j), ketal (3h, 3i), and
To prepare secondary alkylboronate we turned our
amide (3m) can be well tolerated in the reaction. Het- attention to Ni catalysts. The cross-coupling of 4a
erocycles including indole (3k), benzooxazole (3l), with B2pin2 was tested as a model reaction (Table 3).
and chromenone (3n) are also compatible with the Our first experiment with NiBr2·diglyme and ligand
borylation conditions. Nonetheless, the present condi- L7 shows that the desired product 5a was obtained in
tions cannot be used to borylate alkyl iodides, chlor- 20% yield (entry 1). However, after testing several Ni
ides, and tosylates. This reactivity difference can be salts and solvents we failed to improve the reaction
À
used to selectively borylate the C Br bond of 6-chlor- (Supporting Information). Vicic et al. reported that
ohexyl bromide to generate 3c.
ligand L8 may improve Ni-catalyzed cross-coupling.[14]
Furthermore, the Pd-catalyzed method cannot be Besides, Fu et al. favored the use of (i-Pr)2O in their
used to borylate secondary alkyl bromides. As shown Ni-catalyzed reactions.[13e,f] We thus used L8 and (i-
in Scheme 1, when 1o was reacted with B2pin2 under Pr)2O and increased the yield to 61% (entry 2). We
Pd catalysis, the mono-borylated product 3o was ob- also examined a number of other ligands (entries 3–8)
tained in modest isolated yields (45% or 62% de- but only obtained lower yields. We then tested the
pending on the substrate ratio) without any formation idea of using of i-BuOH to facilitate the transmetala-
of 3o’ or 3o’’. On the other hand, when the Cu cata- tion process.[13d] Gratifyingly, we observed a good
lyst was used for the same reaction, a mixture of 3o, yield of 85% (entry 9). Note that by using CuI to re-
3o’, and 3o’’ was obtained in spite of the fact that 1o place NiBr2·diglyme in the optimized conditions,
was added in excess. This experiment confirms that almost no borylation was observed (entry 10). Thus
the Pd- and Cu-catalyzed borylation reactions are dif- the Ni-catalyzed borylation reaction is not caused by
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Alkylboronic Esters from Palladium- and Nickel-Catalyzed Borylation
Table 2. Substrate scope of the Pd-catalyzed borylation.[a]
[a]
The reactions were conducted under the optimized conditions on a 0.5-mmol
scale. Isolated yields are reported.
Scheme 1. Selective borylation. More details can be found in the Supporting Information.
Cu contamination. Moreover, in a control experiment
With the optimized conditions in hand, we exam-
we confirmed that without Ni the reaction did not ined the scope of the Ni-catalyzed borylation reaction
occur (entry 11). Finally, it is important to note that (Table 4). Our results show that cyclic secondary alkyl
no borylation took place when no ligand was added bromides of different ring sizes (5a–5d) can be readily
(entry 12). This behavior is different from the Cu-cat- borylated. Acyclic, as well as bicyclic substrates can
alyzed borylation of secondary alkyl halides, because also be employed (5e–5h). As to the functional
the use of ligand is helpful but not obligatory for the groups, the reaction tolerates ether (5i, 5j, 5s), pro-
Cu-catalyzed reaction to occur.
tected amine (5k, 5l), fluoro (5n), trifluoromethyl
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Table 3. Ni-catalyzed borylation of cyclohexyl bromide.[a]
Entry
Ni salt (4 mol%)
Ligand (5 mol%)
Base
Solvent (2 mL)
1,4-dioxane
A
N
N
R
E
G
Yield of 5a [%][a]
1
2
3
4
5
6
7
8
NiBr2·diglyme
NiBr2·diglyme
NiBr2·diglyme
NiBr2·diglyme
NiBr2·diglyme
NiBr2·diglyme
NiBr2·diglyme
NiBr2·diglyme
NiBr2·diglyme
CuI
L7
L8
L9
L10
L11
L12
L13
L14
L8
KO-t-Bu
KO-t-Bu
KO-t-Bu
KO-t-Bu
KO-t-Bu
KO-t-Bu
KO-t-Bu
KO-t-Bu
KO-t-Bu
KO-t-Bu
KO-t-Bu
KO-t-Bu
20
61
24
6
12
3
32
25
N
E
9[b]
10[d]
11
12
85 (82)[c]
trace
0
L8
L8
–
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
G
–
NiBr2·diglyme
trace
[a]
GC yields after 24 h.
[b]
[c]
[d]
1.8 equiv. i-BuOH was added.
Isolated yield in the parenthesis.
4 mol% CuI were added.
(5o), methylenedioxy (5p), and furan (5q). Both tained the cyclopentylmethyl boronate 6c as the only
2
3
À
À
CACHTUNGTRENNUNG(sp ) Cl and CACHTUNGTRENNUNG(sp ) Cl bonds are compatible with product. This observation appears consistent with the
the reaction (5r, 5t), thus opening the possibility for possibility that an initially formed alkyl radical cycliz-
additional modifications through other cross-coupling es before reacting with Ni.[13,15] On the other hand,
reactions at the halogenated positions. It is important when the Pd catalyst was used we obtained a complex
to note that the reaction can be easily scaled up to mixture. Furthermore, when (S)-(2-bromopropyl)ben-
gram quantities without any loss in yield (5r). More- zene [prepared from (R)-1-phenylpropan-2-ol[16]] was
over, the optimized conditions can also be used to borylated with the NiBr2·diglyme/L8 catalyst, a race-
borylate primary alkyl bromides (3a). Nonetheless, mic product was obtained, again suggesting the in-
our tests show that secondary alkyl iodides, chlorides, volvement of an alkyl radical intermediate
and tosylates cannot be borylated by using the pres- (Scheme 3). Several attempts were then made to use
ent conditions.
chiral ligands (e.g., L13 and L14) to control the ste-
We consider the mechanism of the present boryla- reoselectivity of the borylation process (Scheme 3),
tion reactions to be similar to that of the previously but the product was still a racemic mixture. Nonethe-
reported Pd- and Ni-catalyzed cross-coupling of ali- less, because the addition of a ligand is necessary in
phatic electrophiles with organoboronic acids.[12,13] Al- Ni-catalyzed borylation, we believe that further opti-
though more experimental studies are underway to mization of the ligand and reaction conditions may
obtain a full understanding of the mechanism, some allow the synthesis of alkylboronates with stereocon-
preliminary tests showed interesting results. First, we trol.
examined the borylation of 6-bromohex-1-ene
In conclusion, we have developed Pd- and Ni-cata-
(Scheme 2). When the Ni catalyst was used, we ob- lyzed cross-coupling reactions of unactivated alkyl
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Adv. Synth. Catal. 2012, 354, 1685 – 1691

Alkylboronic Esters from Palladium- and Nickel-Catalyzed Borylation
Table 4. Substrate scope of Ni-catalyzed borylation.[a]
[a]
The reactions were conducted under the optimized conditions on a 0.5-mmol
scale. Isolated yields are reported.
On a 5.0-mmol scale.
[b]
bromides with diboron reagents. These reactions can limited to Cu catalysis, but rather a general reaction.
be used to prepare primary and secondary alkylbor- Because the selectivity of the Pd- and Ni-catalyzed
onic esters with diverse skeletons and functional borylation reactions is different from that of the Cu-
groups. This finding indicates that the cross-coupling catalyzed one, the Pd- and Ni-versions of the boryla-
of aliphatic electrophiles with diboron reagents is not tion reactions may prove to be complementary to the
Cu-catalyzed method. It is worthyof note that in the
Ni-catalyzed synthesis of secondary alkylboronic
esters, the addition of nitrogen ligands is ncessary. By
contrast, addition of ligand is not obligatory in the
Cu-catalyzed borylation of secondary aliphatic elec-
trophiles. This finding hints at the unique opportunity
of using ligands to control the stereoselectivity in Ni-
catalyzed borylation reactions.
Experimental Section
Typical Procedure (Table 2)
Scheme 2. Borylation of 6-bromohex-1-ene. More details
can be found in the Supporting Information.
In air, Pd2dba3 (6.9 mg, 0.0075 mmol), P
(7.5 mg, 0.03 mmol), NaOMe (81 mg, 1.5 mmol), and bis(pi-
ACHTUNGRTEN(UNNG t-Bu)2Me·HBF4
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Scheme 3. Attempts to prepare chiral boronates.
nacolato)diboron (190 mg, 0.75 mmol) were added to
a Schlenk tube equipped with a stir bar. The vessel was
evacuated and filled with argon (three cycles). 1,4-Dioxane
(2.00 mL) and an alkyl bromide (0.50 mmol) were added in
turn by syringe under an argon atmosphere (if the alkyl bro-
mide is a solid, it was added along with the Pd2dba3). The
resulting reaction mixture was stirred vigorously at 258C for
24 h. The reaction mixture was then diluted with EtOAc, fil-
tered through silica gel with copious washings (Et2O or
EtOAc), concentrated, and purified by column chromatog-
raphy.
Okuda, T. Yamori, H. Tsumoto, H. Nakagawa, N.
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Typical Procedure (Table 4)
In air, NiBr2·diglyme (7.0 mg, 0.02 mmol), 4,4’,4“-tri-tert-
butyl-2,2’:6’,2”-terpyridine (10.0 mg, 0.025 mmol), KO-t-Bu
(112 mg, 1.0 mmol), and bis(pinacolato)diboron (228 mg,
0.90 mmol) were added to a Schlenk tube equipped with
a stir bar. The vessel was evacuated and filled with argon
(three cycles). (i-Pr)2O (2.0 mL) and i-BuOH (82 mL,
0.9 mmol) were added in turn by syringe under an argon at-
mosphere in an ice bath and the mixture was stirred for
5 min. Then an alkyl bromide was added by syringe (if the
alkyl bromide is a solid, it was added along with the
NiBr2·diglyme). The resulting reaction mixture was stirred
vigorously at 608C for 24 h. The reaction mixture was then
diluted with EtOAc, filtered through silica gel with copious
washings (Et2O or EtOAc), concentrated, and purified by
column chromatography.
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Acknowledgements
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This study was supported by the national “973” grants from
the
Ministry
of
Science
and
Technology
(No.
2011CB965300). We thank Prof. Todd B. Marder and Prof.
Patrick G. Steel for their insightful suggestions.
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