Nickel-Catalyzed Borylation of Aryl- and Benzyltrimethylammonium Salts via C-N Bond Cleavage

Article abstract of DOI:10.1021/acs.joc.5b02557

By developing a mild Ni-catalyzed system, a method for direct borylation of sp² and sp³ C-N bonds has been established. The key to this hightly efficient C-N bond borylative cleavage depends on the appropriate choice of the nickel catalyst Ni(COD)₂, ICy·HCl as a ligand, and the use of 2-ethoxyethanol as the cosolvent. This transformation shows good functional group compatibility and can serve as a powerful synthetic tool for gram-scale synthesis and late-stage C-N borylation of complex compounds.

Full text of DOI:10.1021/acs.joc.5b02557

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Featured Article
Nickel-Catalyzed Borylation of Aryl- and
Benzyltrimethylammonium Salts via C-N Bond Cleavage
Jiefeng Hu, Heqing Sun, Wangshui Cai, Xinghui Pu, Yemin Zhang, and Zhuangzhi Shi
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.5b02557 • Publication Date (Web): 02 Dec 2015
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Nickel-Catalyzed Borylation of Aryl- and Benzyltrimethylammoni-
um Salts via C-N Bond Cleavage
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Jiefeng Hu, Heqing Sun, Wangshui Cai, Xinghui Pu, Yemin Zhang and Zhuangzhi Shi*
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State Key Laboratory of Coordination Chemistry, Collaborative Innovation Center of Chemistry for Life Sciences, School of
Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China
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ABSTRACT: By developing a mild Niꢀcatalyzed system, a method for direct borylation of sp2 and sp3 CꢀN bonds has been estabꢀ
lished. The key to this hightly efficient CꢀN bond borylative cleavage depends on the appropriate choice of the nickel catalyst
Ni(COD)2, ICy•HCl as a ligand and the use of 2ꢀethoxyethanol as the coꢀsolvent. This transformation shows good functional
group compatibility and can serve as a powerful synthetic tool for gramꢀscale synthesis and lateꢀstage CꢀN borylation of complex
compounds.
■ INTRODUCTION
The transitionꢀmetalꢀcatalyzed functionalization of unreactive bonds has become one of the most powerful protocols available to
practitioners of chemical synthesis.1 CꢀN bonds are one of the most abundant and unreactive bonds in organic molecules, and the
selective cleavage of them represents a challenge in the field of organometallic chemistry.2 Since Wenkert et al. uncovered the first
Niꢀcatalyzed Kumada coupling of aryltrimethylammonium iodide salts in 1988,3 other types of CꢀC bond crossꢀcoupling reactions
via CꢀN bond cleavage including Suzuki coupling4 and Negishi coupling5 have been developed in succession. Although the
rutheniumꢀcatalyzed direct arylation of CꢀN bond in aniline derivatives has also been developed in this context, the requirement of
the substrates bearing an ortho directing group has restricted their general use.6 In addition to the CꢀC bond formation reactions,
most recently, Garg and Houk et al. reported an important breakthrough for the conversion of amides to esters via nickelꢀcatalyzed
activation of amide CꢀN bonds.7
Aryl and alkyl substituted boronic acid and their derivatives are versatile synthetic intermediates.8 Among the routes to these
compounds, the borylation of CꢀH,9 CꢀO,10 CꢀF,11 and CꢀC12 bonds have shown promise because it bestows these inert functional
groups with the synthetic versatility. In 2014, Tobisu and Chatani developed the first Niꢀcatalyzed borylative cleavage of CꢀN
bonds in Nꢀaryl amides and carbamates with fused aromatic system such as napthalenes, anthracenes and phenanthrenes at high
temperature.13 Although polycyclic aromatic amine derivatives are not necessarily ideal substrates for certain transformations, with
some not readily available, the transformation is highly important for the construction of CꢀB bonds from this nonconventional
synthetic strategy. N,Nꢀdimethylamino functional groups are widely represented in biologically active natural products, medicines
and dyes (a small selection of which are shown in Scheme 1), and many of them are commercially available at low prices. Thereꢀ
fore, mild methods for borylative cleavage of these sp2 and sp3 CꢀN bonds will not only expand the utility of the NMe2 substituent
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as a functional group, but also provide a route to make these readily available compounds to useful synthetic intermediates and
commercial chemicals. In order to achieve this goal, several difficulties need to be overcome, in particular the issues of selective
cleavage of a CꢀN bond in a complex molecule, since, (1) generally, the CꢀN bond scission requires a relatively high activation
energy because of the strength and stability of its linkage; (2) the discrimination of different types of CꢀN bonds is challenging; (3)
the selective cleavage of CꢀN bonds instead of CꢀH,9 CꢀO10 and Cꢀhalogen14 bonds is hard to control; and (4) elimination process in
sp3 CꢀN bond cleavage is a significant impediment for crossꢀcoupling.15 Here, we report our results on nickelꢀcatalyzed highly
chemoꢀ and regioselective CꢀN bond borylation by activating ammonium salts under mild and scalable conditions. This system is
effective not only for high functionalꢀgroup tolerance of arylamines but also for the primary, secondary and even tertiary benzylaꢀ
mines. Moreover, application of this method in the preparation of some important organoboronate intermediates showcases the
strategic opportunity to utilize this transformation in the synthesis of biologically active compounds.
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Scheme 1. Nature Products, Drugs and Dyes Involving NMe2 Groups
■ RESULTS AND DISCUSSION
Initial studies involved the evaluation of the selective CꢀN borylation of 4ꢀmethoxyꢀN,Nꢀdimethylaniline (1a) (Table 1). The exꢀ
periments were performed with the corresponding aryltrimethylammonium triflate 2a which was easily prepared in quantitative
yield via methylation of 1a, and bis(pinacolato)diboron (B2Pin2, 3a) in the presence of 5 mol% Ni(COD)2, 10 mol% IMes•HCl (L1)
and 2.0 equiv tBuONa, at 50 oC under an Ar atmosphere in toluene. We indeed observed the desired product 4aa in 5% yield after
12 h in GCꢀMS without any CꢀO bond cleavage byproducts (Table 1, entry 1). A variety of alcohols were investigated as potential
promoters, and 2ꢀethoxyethanol (EE) showed the best result increasing the yield to 16% (Table 1, entry 2). Among various NHC
ligands, a dramatic effect of ICy•HCl (L3) is notable, affording 78% yield of 4aa (Table 1, entries 3ꢀ5). Under these conditions,
both toluene and EE (v/v=1:1) were indispensable for this coupling. Changing the coꢀsolvent ratio or replacing EE with MeOH or
nBuOH resulted in much lower yields(Table 1, entries 6ꢀ10). tBuOLi was not as effective as tBuONa (Table 1, entry 11), and nearly
quantitative yield was observed by employing tBuOK as the base (Table 1, entry 12). To our delight, other nickel sources as catalyst
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such as Ni(OTf)2 was also proven successful in this coupling reaction with a high reactivity (Table 1, entries 13ꢀ14). Notably, deꢀ
creasing the Ni(COD)2 loading to 1 mol% still resulted in a good yield (Table 1, entry 15) and no product is observed in the absence
of Ni catalyst (Table 1, entry 16).
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Table 1. Reaction Developmenta
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yield
entry
[M]
L
Base
solvent
(%)b
5
1
2
3
4
5
6
7
8
9
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
tBuONa
tBuONa
tBuONa
tBuONa
tBuONa
tBuONa
tBuONa
tBuONa
Toluene
Toluene/EE (1:1)
Toluene/EE (1:1)
Toluene/EE (1:1)
Toluene/EE (1:1)
Toluene
L1
L1
L2
L3
L4
L3
L3
L3
L3
L3
L3
16
18
78
25
33
EE
54
Toluene/EE (3:1)
68
tBuONa Toluene/MeOH (1:1)
tBuONa Toluene/nBuOH (1:1)
tBuOLi
42
10 Ni(COD)2
71
11 Ni(COD)2
12 Ni(COD)2 L3 tBuOK
Toluene/EE (1:1)
Toluene/EE (1:1)
Toluene/EE (1:1)
Toluene/EE (1:1)
Toluene/EE (1:1)
Toluene/EE (1:1)
65
99(94)c
13
Ni(OTf)2
tBuOK
tBuOK
tBuOK
tBuOK
91
L3
L3
L3
L3
14
NiCl2
18
15d Ni(COD)2
16
82
ꢀ
0
aReaction conditions: 2a (0.20 mmol), 3a (0.50 mmol), 5 mol% of catalyst, 10 mol% of ligand, 2.0 equiv of base in solvent (2.0 mL), 16 h,
under Ar. bDetermined by GC analysis. cYield. dUsing 1 mol% Ni(COD)2 and 2 mol% L3. EE = 2ꢀethoxyethanol.
To evaluate the utility of the Niꢀcatalyzed borylation of CꢀN bonds, a series of N,Nꢀdimethylanilines were tested in Table 2. Gratifyingly,
a wide range of arylammonium triflates that incorporate electronꢀ neutral, electronꢀdonating and electronꢀwithdrawing substituents at the
ortho, meta, and para positions were readily tolerated (4baꢀ4oa). Among them, sterically hindered substrate 2e resulted in good yield.
Notably, this method can selectively activate the CꢀN bond in the presence of ether groups (4ga and 4ha) and hydroxyl group (4ia)
.
Moreover, the unique selectivity toward ammonium triflate was further corroborated by the presence of other types of CꢀN bonds
such as amide, BocNH and NH2 groups (4jaꢀ4la). Transitionꢀmetalꢀcatalyzed orthoꢀCꢀH borylation is a general process in the presꢀ
ence of directingꢀgroups such as benzamide and benzoic acid.16 In our conditions, the directingꢀgroupꢀcontaining substrates 4naꢀ
4oa can also selectively cleave CꢀN bonds, avoiding the catalyst to bind the directing groups. It's noted that only fluoroꢀsubstituted
phenylammonium triflate 4ma can be selectively borylated at the CꢀN bond, other halideꢀsubstituents such as aryl chlorides underꢀ
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went borylation at both the CꢀCl and CꢀN bonds. In addition, polycyclic and hetero cyclic substrates were also compatible (4paꢀ4qa).
To our delight, the ꢀNMe2 groups in drugs and dyes such as Padimate (2r), Norneostigmine (2s) and Methyl Yellow (2t) bearing ester,
carbamate and diazenyl groups can be converted to the corresponding products successfully. Diborylated units are versatile synthetꢀ
ic intermediates, and practical and economical synthesis of them from the readily available chemicals is undoubtedly an ideal route.
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We observed that the desired borylation also took place when using the industrial materials such as Methane Base (2u),
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CTK2B1386 (2v), Leuco Malachite Green (2w) and BF003152 (2x), affording the corresponding products 4uaꢀ4xa in good to exꢀ
cellent yields.
Table 2. Ni-Catalyzed Borylation of Aryl C-N Bondsa
t
aReaction conditions: 2 (0.20 mmol), 3a (0.50 mmol), 5 mol% of Ni(COD)2, 10 mol% of L3, BuOK (0.4 mmol) in 2.0 mL toluene/EE
(1:1) at 40 oC, 12 h, under Ar. bUsing phenyltrimethylammonium iodide as the substrate. c1.00 mmol 3a.
Our nickelꢀcatalyzed system is not limited to the use of B2Pin2 as the sole borylating agent. Under the optimal conditions, reacꢀ
tions with bis(hexylene glycolato)diboron (3b) and bis(neopentyl glycolato)diboron (3c) also provided the aryl boronic esters 4ab
and 4ac in 73% and 92% yields, respectively (Scheme 2). However, when pinacolborane (3d) and 9ꢀborabicyclo[3.3.1]nonane (9ꢀ
BBN dimer, 3e) were employed, no desired products were detected, which might be attributed to the lack of the required BꢀB bonds
in borylating agents for the transformation.
Scheme 2. Investigation of Different Borylating Agents
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Further investigation revealed that benzylamines could also serve as suitable coupling partners with B2Pin2 (3a) (Table 3). Simiꢀ
lar as the high functionalꢀgroup tolerance in arylamine substituents, this substrate scope was also found to be very wide. Products
containing methyl, ether, fluoro and ester substituents were formed in high yields. In the case of secondary benzylamines, βꢀ
hydrogens posed no problems. Moreover, the βꢀamino acid derivative 6p is compatible with this method, giving 7pa in an accepted
yield of 31%. A particularly noteworthy point of our catalytic system is the first time report of tertiary CꢀN bond activation, as obꢀ
served by the borylation of substrates 6qꢀ6s to produce desired product in moderate to good yields.
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Table 3. Ni-Catalyzed Borylation of Benzylic C-N Bondsa
NMe3OTf
R1
BPin
5 mol% Ni(COD)2
10 mol% L3
2.0 equiv tBuONa
Toluene/EE (1:1)
50oC, Ar
R1
R2
R2
+
B2Pin2
R
R
3a
6
7
Primary C-N bond cleavage:
BPin
BPin
BPin
OMe BPin
Me
Me
Me
7aa, 76% (69%)b
7ba, 71%
BPin
7ca, 72%
7da, 73%
BPin
F
BPin
BPin
MeO
O
O
F
MeO
7ea, 88%
7fa, 90%
7ga, 70%
7ha, 73%
Secondary C-N bond cleavage:
BPin Me BPin
BPin
Me
BPin
Me
Me
Me
MeO
F
7ia
7ja
7ka
7la
, 79%
, 75%
BPin
, 90%
, 76%
Me BPin
Me
BPin
BPin
COOMe
Ph
Ph
(from DL-
β-Phe-OH)
7ma
, 73%
7na
7oa
7pa
, 74%
, 72%
, 31%
Tertiary C-N bond cleavage:
Ph BPin
Ph BPin
Ph BPin
Me
7ra, 60%
Ph BPin
Me Me
Et
7qa, 74%
7sa, 63%
7ta, 50%
t
aReaction conditions: 6 (0.20 mmol), 3a (0.50 mmol), 5 mol% of Ni(COD)2, 10 mol% of L3, BuONa (0.4 mmol) in 2.0 mL toluene/EE
(1:1) at 50 oC, 12 h, under Ar. bUsing tBuOK.
A major benefit of this mild, highly selective CꢀN bond borylation procedure is its amenability to gramꢀscale and lateꢀstage synꢀ
thetic applications (Scheme 3). To demonstrate this potential, complex molecule 8 containing a number of different types of CꢀO
and CꢀN bonds was subjected to our borylation protocol and the corresponding arylammonium triflate 9 can be selectively
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borylated at CꢀNMe3 bond position to yield aryl boronic ester 10 in 86% yield. Subsequent copperꢀmediated nucleophilic 18F fluorꢀ
ination of 10 can provide the translocator protein (TSPO) PET ligand [18F]DAA1106.17 Nickelꢀcatalyzed ringꢀopening and crossꢀ
coupling of aziridines has been developed recently.18 Remarkably, our optimaized method provide an effective tool to cleave the
larger rings in azaheterocyclic compounds. By employing the indoline and 1,2,3,4ꢀtetrahydroquinoline derivatives 11a and 11b as
substrates and B2Pin2 (3a) as the borylation reagent, the ringꢀopened products 13aa-13ba can be generated in 35ꢀ42% yields at the
current stage (Scheme 4).
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Scheme 3. Gram-Scale Synthesis and Late-Stage Borylative C-N Bond Cleavage of Complex Molecule
Scheme 4. Ring-Opening via Borylative Cleavage of C-N Bonds
Fu and others proved that nickelꢀcatalyzed Miyauraꢀtype borylation of aryl and alkyl halides was proposed to be a radical inꢀ
volved mechanism.19 However, our reaction proceeds with comparable efficiency in the presence of 1.0 equiv of TEMPO, DHA or
BHT as the radical inhibitors. Moreover, a radicalꢀclock experiment using ammonium triflate 14 can further rule out the radical
pathway (Scheme 5).
Scheme 5. Mechanistic Experiments
NMe3OTf
BPin
"standard conditions"
+ 1.0 equiv TEMPO, 56%
+ 1.0 equiv DHA, 91%
+ 1.0 equiv BHT, 89%
B2Pin2 (3a)
MeO
MeO
2a
4aa
NMe3OTf
BPin
"standard conditions"
BPin
+
B2Pin2 (3a)
, n.d
16
, 55%
15
14
Scheme 6. Borylation of Chiral Substrate
Bpin
Me
NMe3OTf
3a
)
B2Pin2
(
Me
(S)-6i
(R)-7ia
"standard conditions"
Using dioxane/iEE(2.5 eq)
78%, 48% ee
71%, 64% ee
Using dioxane/iBuOH(2.5 eq) 65%, 82% ee
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Watson and coꢀworkers previously uncovered that Niꢀcatalyzed process for the stereospecific crossꢀcoupling of benzylic ammoꢀ
nium salts and boronic acids proceed via an SN2 mechanism.4b When (S)ꢀ6i (99% ee) was allowed to react with B2Pin2 (3a) in our
standard conditions, only (R)ꢀ7ia of 48% ee was observed in 78% yield (Scheme 6).20 A further improved screening revealed that
6
7
8
i
solvent affects the chirality transfer with dioxane as solvent and 2.5 equiv BuOH as additive providing (R)ꢀ7ia in good enantiꢀ
9
ospecificity (65% yield, 82% ee). This result is consistent with the inversion of configuration observed in stereospecific CꢀC bond
formation cross couplings.15c, 21 On the basis of these investigations, we have hypothesized that the mechanism outlined in Scheme
7 is operative when ammonium triflates 2 or 6 are employed as electrophiles. The oxidative addition of the nickel catalyst into the
benzylic C−N bond likely takes place via an SN2 mechanism, leading to inversion of configuration of the benzylic stereocenter. The
specific role of the coꢀsolvent 2ꢀethoxyethanol (EE) is to generate the anionic adduct of borylating agent B from 3 in the presence
of KOtBu, which is the key to success for the transmetallation process in this catalytic cycle.22
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Scheme 7. Proposed Catalytic Cycle
In summary, we have developed a mild Niꢀcatalyzed system, which is capable to activate aryl and benzyl ammonium bonds for
CꢀN bond borylation to produce various organoboronates.23 In view of the widespread ꢀNMe2 group and its precursors in chemicals,
this method offers a meaningful tool to enable them as valuable building blocks. This transformation showed exceptional functional
group tolerance, high efficiency and excellent chemoselectivity. Due to these advantages, this reaction should be of high synthetic
value.
■ EXPERIMENTAL SECTION
All new compounds were fully characterized. NMRꢀspectra were recorded either a 300 or 400 MHz spectrometer. HRMS spectra
were recorded on a spectrometer with an ESI source. GCꢀMS spectra were recorded on a spectrometer with an EI source. All reacꢀ
tions were carried out in flameꢀdried reaction vessels with Teflon screw caps under argon. Unless otherwise noted, materials obꢀ
tained from commercial suppliers were used without further purification. Ni(COD)2, 2ꢀethoxyethanol, toluene and ICy•HCl were
purchased from Acros. KOtBu and (Bpin)2 was purchased from SigmaꢀAldrich.
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General Procedure for Preparation of Ammonium Triflates. The preparation of the dimethyl amines were described according
to EscheweilerꢀClarke conditions24ꢀ25. The ammonium triflates were prepared according to the literatures26. To a solution of 4ꢀ
methoxyaniline (1.2 g, 10.0 mmol, 1.0 eq.) in MeOH (15 mL) under Ar were added formic acid to adjust pH to 3ꢀ4. NaBH3CN (0.9
g, 15.0 mmol, 1.5 eq.) was added to the reaction mixture and stirred for 10 min at room temperature. The mixture was cooled in a 0
oC iceꢀwater bath, and formaldehyde (18 mL, 500 mmol, 50 eq.) was added slowly via a syringe and the mixture was allowed to
warm to rt and stirred at 35 oC under Ar for 16 h. The resulting mixture was concentrated and the solution of K2CO3(5 M) was addꢀ
ed to pH≈12. The aqueous layer was extracted with DCM (3 x 50 mL). The combined organic layer was dried over Na2SO4.The
filtrate was concentrated and the crude product was purified by column chromatography on silica gel (DCM: MeOH = 20 : 1).
Dimethylamine (5 mmol, 1.0 equiv) was dissolved in Et2O (10 mL). MeOTf (6.5 mmol, 1.3 equiv) was added dropwise at 0 °C.
After complete addition the reaction mixture was stirred for an additional 15ꢀ60 minutes at 0 °C. The solution was concentrated and
washed with Et2O (2 x 20 mL). The resulting compounds were dried under vacuum to give salt.
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N,N,N,3,4-Pentamethylbenzenaminium trifluoromethanesulfonate (2d). A white solid (1.4 g, 92%). H NMR (400 MHz,
DMSO) δ 7.73 (d, J = 2.7 Hz, 1H), 7.61 (dd, J = 8.5, 2.9 Hz, 1H), 7.34 (d, J = 8.6 Hz, 1H), 3.53 (s, 9H), 2.29 (s, 3H), 2.24 (s, 3H).
13C{1H} NMR (101 MHz, DMSO) δ 145.0, 138.6, 138.4, 130.5, 120.9, 117.3, 56.3, 19.6, 18.7. HRMS m/z (ESI) calcd for C11H18N
(M ꢀ OTf)+ 164.1434, found 164.1434.
3-(tert-Butyl)-N,N,N-trimethylbenzenaminium trifluoromethanesulfonate (2f). A white solid (1.5 g, 88%). 1H NMR (400 MHz,
DMSO) δ 7.87 (s, 1H), 7.75 (dd, J = 8.1, 2.6 Hz, 1H), 7.65 – 7.49 (m, 2H), 3.61 (s, 9H), 1.34 (s, 9H); 13C{1H} NMR (101 MHz,
DMSO) δ 153.3, 147.2, 129.6, 126.8, 117.3, 56.4, 35.1, 30.9. HRMS m/z (ESI) calcd for C13H22N (M ꢀ OTf)+ 192.1747, found
192.1748.
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2-(Benzyloxy)-N,N,N-trimethylbenzenaminium trifluoromethanesulfonate (2g). A white solid (1.8 g, 92%). H NMR (400
MHz, DMSO) δ 7.80 (dd, J = 8.5, 1.2 Hz, 1H), 7.59 (ddd, J = 8.3, 7.6, 2.9 Hz, 3H), 7.53 – 7.37 (m, 4H), 7.18 (ddd, J = 8.6, 7.5, 1.4
Hz, 1H), 5.38 (s, 2H), 3.64 (s, 9H); 13C{1H} NMR (101 MHz, DMSO) δ 150.6, 135.5, 133.5, 131.9, 128.8, 128.5, 121.9, 121.4,
115.8, 71.0, 55.1. HRMS m/z (ESI) calcd for C16H20NO (M ꢀ OTf)+ 242.1539, found 242.1541.
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3-(tert-Butyl)-N,N,N-trimethylbenzenaminium trifluoromethanesulfonate (2h) . A black solid (1.3 g, 75%). H NMR (400
MHz, DMSO) δ 7.67 – 7.50 (m, 3H), 7.35 – 7.19 (m, 1H), 5.31 (s, 2H), 3.59 (s, 9H), 3.41 (s, 3H); 13C{1H} NMR (101 MHz,
DMSO) δ 157.4, 148.2, 130.9, 117.0, 113.3, 109.4, 94.1, 56.3, 55.9. HRMS m/z (ESI) calcd for C11H18NO2 (M ꢀ OTf)+ 196.1332,
found 196.1332.
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4-Hydroxy-N,N,N-trimethylbenzenaminium trifluoromethanesulfonate (2i). A colorless oil (0.9 g, 60%). H NMR (400 MHz,
DMSO) δ 10.17 (s, 1H), 7.81 – 7.70 (m, 2H), 6.99 – 6.87 (m, 2H), 3.55 (s, 9H); 13C{1H} NMR (101 MHz, DMSO) δ 158.1, 138.7,
121.6, 115.81, 56.5. HRMS m/z (ESI) calcd for C9H14NO (M ꢀ OTf)+ 152.1070, found 152.1069.
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1-Acetyl-N,N,N-trimethylindolin-5-aminium trifluoromethanesulfonate (2j). A white solid (1.7 g, 92%). H NMR (400 MHz,
DMSO) δ 8.10 (d, J = 9.0 Hz, 1H), 7.87 (s, 1H), 7.72 (dd, J = 9.0, 2.6 Hz, 1H), 4.17 (t, J = 8.6 Hz, 2H), 3.57 (s, 9H), 3.22 (t, J = 8.5
Hz, 2H), 2.18 (s, 3H); 13C{1H} NMR (101 MHz, DMSO) δ 169.3, 143.7, 142.0, 133.9, 119.3, 117.3, 115.4, 56.6, 48.6, 27.4, 23.8.
HRMS m/z (ESI) calcd for C13H19N2O(M ꢀ OTf)+ 219.1492, found 219.1493.
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1-Acetyl-N,N,N-trimethylindolin-5-aminium trifluoromethanesulfonate (2k). A white solid (1.2 g, 65%). H NMR (400 MHz,
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δ 152.6, 140.9, 140.7, 120.9, 118.3, 79.8, 56.4, 28.0. HRMS m/z (ESI) calcd for C14H23N2O2 (M ꢀ OTf)+ 251.1754, found 251.1751.
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4-amino-N,N,N-trimethylbenzenaminium trifluoromethanesulfonate (2l). A white solid (0.5 g, 30%). H NMR (400 MHz,
DMSO) δ 7.71 (d, J = 9.3 Hz, 2H), 6.84 (d, J = 9.3 Hz, 2H), 3.53 (s, 9H)
;
13C{1H} NMR (101 MHz, DMSO) δ 122.7, 122.2,
120.8, 119.0, 56.59.
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4-Fluoro-N,N,N-trimethylbenzenaminium trifluoromethanesulfonate (2m). A white solid (1.4 g, 94%). H NMR (400 MHz,
DMSO) δ 8.17 – 7.92 (m, 2H), 7.50 (t, J = 8.7 Hz, 2H), 3.72 – 3.55 (m, 9H); 13C{1H} NMR (101 MHz, DMSO) δ 163.1 (d, J = 11.1
Hz), 160.7, 143.3, 123.2 (d, J = 9.0 Hz), 116.8, 116.6, 56.6. HRMS m/z (ESI) calcd for C9H13FN (M ꢀ OTf)+ 154.1027, found
154.1031.
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N,N,N-Trimethyl-4-(methylcarbamoyl)benzenaminium trifluoromethanesulfonate (2n) A white solid (1.1 g, 64%). H NMR
(400 MHz, DMSO) δ 8.66 (d, J = 4.0 Hz, 1H), 8.17 – 7.97 (m, 4H), 3.63 (d, J = 7.2 Hz, 9H), 2.81 (d, J = 4.5 Hz, 3H); 13C{1H}
NMR (101 MHz, DMSO) δ 170.0, 154.1, 140.9, 133.9, 125.9, 61.6, 31.5. HRMS m/z (ESI) calcd for C11H17N2O (M ꢀ OTf)+
193.1335, found 193.1336.
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3-Carboxy-N,N,N-trimethylbenzenaminium trifluoromethanesulfonate (2o). A white solid (1.5 g, 91%). H NMR (400 MHz,
DMSO) δ 13.64 (s, 1H), 8.41 (d, J = 1.4 Hz, 1H), 8.26 (dd, J = 8.3, 2.6 Hz, 1H), 8.12 (d, J = 7.8 Hz, 1H), 7.79 (t, J = 8.1 Hz, 1H),
3.65 (s, 9H); 13C{1H} NMR (101 MHz, DMSO) δ 166.0, 147.4, 132.6, 130.6, 125.0, 121.1, 56.3.
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N,N,N-Trimethyldibenzo[b,d]furan-2-aminium trifluoromethanesulfonate (2p). A white solid (1.7 g, 90%). H NMR (400
MHz, DMSO) δ 8.44 (dd, J = 14.3, 5.5 Hz, 2H), 8.28 (d, J = 7.7 Hz, 1H), 8.05 (dd, J = 8.8, 2.4 Hz, 1H), 7.82 (d, J = 8.3 Hz, 1H),
7.64 (dd, J = 8.3, 7.4 Hz, 1H), 7.50 (t, J = 7.5 Hz, 1H), 3.72 (s, 9H); 13C{1H} NMR (101 MHz, DMSO) δ 156.8, 154.9, 146.2, 128.9,
124.8, 123.8, 122.4, 115.6 (s), 112.0, 105.3, 56.9. HRMS m/z (ESI) calcd for C15H16NO2 (M ꢀ OTf)+ 226.1226, found 226.1229.
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9-Ethyl-N,N,N-trimethyl-9H-carbazol-3-aminium trifluoromethanesulfonate (2q) . A white solid (1.6 g, 80%). H NMR (400
MHz, DMSO) δ 8.82 (d, J = 2.5 Hz, 1H), 8.32 (d, J = 7.8 Hz, 1H), 8.08 (dd, J = 9.2, 2.7 Hz, 1H), 7.86 (d, J = 9.2 Hz, 1H), 7.71 (d,
J = 8.2 Hz, 1H), 7.56 (t, J = 7.7 Hz, 1H), 7.33 (t, J = 7.5 Hz, 1H), 4.53 (q, J = 6.9 Hz, 2H), 3.75 (s, 9H), 1.33 (t, J = 7.1 Hz, 3H);
13C{1H} NMR (101 MHz, DMSO) δ 140.5, 139.3, 138.9, 126.9, 121.9, 120.9, 119.5, 117.6, 112.5, 110.0, 109.8, 57.0, 37.2, 13.7.
HRMS m/z (ESI) calcd for C17H21N2 (M ꢀ OTf)+ 253.1699, found 253.1701.
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4-((Isopentyloxy)carbonyl)-N,N,N-trimethylbenzenaminium trifluoromethanesulfonate (2r). A white solid (1.5 g, 75%). H
NMR (400 MHz, DMSO) δ 8.20 – 8.09 (m, 4H), 4.36 (t, J = 6.6 Hz, 2H), 3.35 (s, 9H), 1.81 – 1.68 (m, 1H), 1.63 (q, J = 6.7 Hz, 2H),
0.94 (d, J = 6.6 Hz, 6H); 13C{1H} NMR (101 MHz, DMSO) δ 164.3, 150.4 131.3, 130.7, 121.3, 63.8, 56.3, 36.7, 24.7, 22.3. HRMS
m/z (ESI) calcd for C15H24NO2 (M ꢀ OTf)+ 250.1802, found 250.1805.
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N-(3-((Dimethylcarbamoyl)oxy)phenyl)-N,N-dimethylmethanideaminium trifluoromethanesulfonate salt (2s) . A white solid
(1.2 g, 65%). 1H NMR (400 MHz, DMSO) δ 7.90 – 7.77 (m, 2H), 7.65 (t, J = 8.3 Hz, 1H), 7.38 (dd, J = 8.1, 1.5 Hz, 1H), 3.60 (s,
9H), 3.09 (d, J = 10.2 Hz, 3H), 2.94 (s, 3H); 13C{1H} NMR (101 MHz, DMSO) δ 153.4, 151.9, 147.7, 130.5, 124.0, 117.1, 115.0,
56.4, 36.3, 36.1. HRMS m/z (ESI) calcd for C12H19N2O2 (M ꢀ OTf)+ 223.1441, found 223.1443.
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(E)-N,N-Dimethyl-N-(4-(phenyldiazenyl)phenyl)methanideaminium, trifluoromethanesulfonate salt (2t). A yellow solid (0.9 g,
46%). 1H NMR (400 MHz, DMSO) δ 8.22 (d, J = 9.1 Hz, 2H), 8.10 (d, J = 8.7 Hz, 2H), 7.96 (dd, J = 6.3, 2.8 Hz, 2H), 7.65 (d, J =
4.6 Hz, 3H), 3.69 (s, 9H); 13C{1H} NMR (101 MHz, DMSO) δ 151.9, 151.7, 148.6, 132.4, 129.6, 123.6, 122.9, 122.1, 56.5. HRMS
m/z (ESI) calcd for C15H18N3 (M ꢀ OTf)+ 240.1495, found 240.1497.
4,4'-Methylenebis(N,N,N-trimethylbenzenaminium) trifluoromethanesulfonate (2u). A white solid (2.7 g, 93%). 1H NMR (400
MHz, DMSO) δ 7.88 (d, J = 8.3 Hz, 4H), 7.55 (d, J = 8.4 Hz, 4H), 4.10 (s, 2H), 3.56 (s, 18H); 13C{1H} NMR (101 MHz, DMSO) δ
150.7, 148.0, 135.3, 125.8, 61.6.
4,4'-Oxybis(N,N,N-trimethylbenzenaminium) trifluoromethanesulfonate (2v). A white solid (2.6 g, 89%). 1H NMR (400 MHz,
DMSO) δ 8.03 (d, J = 9.3 Hz, 4H), 7.30 (d, J = 9.3 Hz, 4H), 3.63 (s, 18H); 13C{1H} NMR (101 MHz, DMSO) δ 156.5, 142.9, 122.8,
119.7, 56.6.
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4,4'-(Phenylmethylene)bis(N,N,N-trimethylbenzenaminium) trifluoromethanesulfonate (2w). A white solid (1.7 g, 52%). H
NMR (400 MHz, DMSO) δ 7.92 (dd, J = 9.0, 2.0 Hz, 4H), 7.46 – 7.32 (m, 6H), 7.28 (t, J = 7.3 Hz, 1H), 7.15 (d, J = 7.2 Hz, 2H),
5.90 (s, 1H), 3.59 (d, J = 2.3 Hz, 18H); 13C{1H} NMR (101 MHz, DMSO) δ 150.8, 150.2, 147.3, 135.6, 134.0, 132.1, 125.9, 61.6,
59.2.
4,4'-(9H-Fluorene-9,9-diyl)bis(N,N,N-trimethylbenzenaminium) trifluoromethanesulfonate (2x). A white solid (1.8 g, 49%).
1H NMR (400 MHz, DMSO) δ 8.01 (d, J = 7.5 Hz, 2H), 7.87 (d, J = 9.2 Hz, 4H), 7.54 – 7.44 (m, 4H), 7.37 (td, J = 7.5, 1.0 Hz, 2H),
7.31 (d, J = 9.1 Hz, 4H), 3.56 (s, 18H); 13C{1H} NMR (101 MHz, DMSO) δ 148.9, 146.7, 145.9, 128.9, 128.6, 128.5, 125.9, 121.0,
120.8, 63.9, 56.3.
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1-(Benzo[d][1,3]dioxol-5-yl)-N,N,N-trimethylmethanaminium trifluoromethanesulfonate (6f). A white solid (0.9 g, 52%): H
NMR (400 MHz, DMSO) δ 7.10 (d, J = 1.3 Hz, 1H), 7.08 – 6.98 (m, 2H), 6.10 (s, 2H), 4.41 (s, 2H), 3.00 (s, 9H); 13C{1H} NMR
(101 MHz, DMSO) δ 148.83, 147.5, 127.2, 121.6, 112.4, 108.5, 101.6, 67.8, 51.6. HRMS m/z (ESI) calcd for C11H16NO2 (M ꢀ
OTf)+ 194.1176, found 194.1177.
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1-(2,4-Difluorophenyl)-N,N,N-trimethylmethanaminium trifluoromethanesulfonate (6g). A white solid (1.1 g, 65%). 1H NMR
(400 MHz, DMSO) δ 7.68 (td, J = 8.6, 6.6 Hz, 1H), 7.47 (td, J = 10.6, 2.5 Hz, 1H), 7.29 (td, J = 8.4, 2.2 Hz, 1H), 4.57 (s, 2H), 3.07
(s, 9H); 13C{1H} NMR (101 MHz, DMSO) δ 165.1 (d, J = 12.7 Hz), 162.6 (d, J = 12.7 Hz), 136.6 (dd, J = 10.5, 4.4 Hz), 119.0,
112.72 – 112.0 (m), 105.1, 104.8, 104.6, 60.9, 51.8. HRMS m/z (ESI) calcd for C10H14F2N (M ꢀ OTf)+ 186.1089, found 186.1089.
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N,N,N-Trimethyl-1,2,3,4-tetrahydronaphthalen-1-aminium trifluoromethanesulfonate (6n). A white solid (1.0 g, 59%). H
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NMR (400 MHz, DMSO) δ 7.49 (d, J = 7.6 Hz, 1H), 7.43 (t, J = 7.5 Hz, 1H), 7.32 (t, J = 7.5 Hz, 2H), 4.90 (dd, J = 7.1, 3.2 Hz, 1H),
2.99 (s, 9H), 2.76 (dd, J = 8.5, 5.5 Hz, 2H), 2.41 (s, 1H), 2.23 – 2.11 (m, 1H), 2.11 – 1.96 (m, 1H), 1.47 (dd, J = 13.3, 6.9 Hz, 1H);
13C{1H} NMR (101 MHz, DMSO) δ 142.7, 133.5, 130.0, 129.5, 126.9, 125.9, 71.7, 50.6, 27.9, 22.8, 21.0.
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N,N,N-Trimethyl-1-phenyl-2-(p-tolyl)ethan-1-aminium trifluoromethanesulfonate (6o) . A white solid (1.2 g, 60%). H NMR
(400 MHz, DMSO) δ 7.90 (s, 1H), 7.60 – 7.17 (m, 4H), 7.06 – 6.89 (m, 4H), 4.90 (dd, J = 12.3, 3.1 Hz, 1H), 3.70 – 3.57 (m, 1H),
3.49 (t, J = 12.8 Hz, 1H), 3.10 (s, 9H), 2.15 (s, 3H); 13C{1H} NMR (101 MHz, DMSO) δ 135.5, 132.8, 131.0, 130.1, 129.1, 128.8,
77.9, 51.0, 32.2, 20.4.
3-Methoxy-N,N,N-trimethyl-3-oxo-1-phenylpropan-1-aminium trifluoromethanesulfonate (6p). A white solid (1.2 g, 65%). 1H
NMR (400 MHz, DMSO) δ 7.65 (s, 2H), 7.56 – 7.46 (m, 3H), 5.04 (dd, J = 11.1, 4.0 Hz, 1H), 3.64 – 3.49 (m, 2H), 3.47 (s, 3H),
3.02 (s, 9H); 13C{1H} NMR (101 MHz, DMSO) δ 169.2, 131.4, 130.4, 128.9, 72.8, 51.9, 51.0, 33.2. HRMS m/z (ESI) calcd for
C13H20NO2 (M ꢀ OTf)+ 222.1489, found 222.1493.
N,N,N-Trimethyl-2-phenylpropan-2-aminium trifluoromethanesulfonate (6q). A white solid (0.9 g, 55%). 1H NMR (400 MHz,
DMSO) δ 7.85 – 7.72 (m, 2H), 7.57 – 7.46 (m, 3H), 2.94 (s, 9H), 1.90 (s, 6H); 13C{1H} NMR (101 MHz, DMSO) δ 135.4, 129.6,
128.4, 74.4, 49.2, 22.5. HRMS m/z (ESI) calcd for C12H20N (M ꢀ OTf)+ 178.1590, found 178.1589.
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N,N,N-Trimethyl-2-phenylbutan-2-aminium trifluoromethanesulfonate (6r). A white solid (0.7 g, 43%). H NMR (400 MHz,
DMSO) δ 7.60 (d, J = 6.5 Hz, 2H), 7.49 (d, J = 7.2 Hz, 3H), 3.03 (s, 9H), 2.76 (dd, J = 12.9, 6.8 Hz, 1H), 2.26 – 2.06 (m, 1H), 1.95
(s, 3H), 0.84 (t, J = 7.1 Hz, 3H).; 13C{1H} NMR (101 MHz, DMSO) δ 131.4, 130.1, 129.9, 128.8, 79.6, 49.3, 25.5, 19.3, 9.7. HRMS
m/z (ESI) calcd for C12H18N (M ꢀ OTf)+ 176.1434, found 176.1435.
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N,N,N-Trimethyl-1-phenylcyclopropan-1-aminium trifluoromethanesulfonate (6t). A white solid (0.7 g, 40%). H NMR (400
MHz, DMSO) δ 7.73 – 7.63 (m, 2H), 7.49 (d, J = 5.8 Hz, 3H), 3.02 (s, 9H), 2.04 – 1.88 (m, 2H), 1.18 – 1.05 (m, 2H); 13C{1H}
NMR (101 MHz, DMSO) δ 133.9, 133.4, 130.1, 128.6, 58.9, 51.5, 10.1. HRMS m/z (ESI) calcd for C14H22N (M ꢀ OTf)+ 204.1747,
found 204.1748.
3-(N-(2,5-dimethoxybenzyl)acetamido)-N,N,N-trimethyl-4-phenoxybenzenaminium (9). To a solution of N1,N1ꢀdimethylꢀ4ꢀ
phenoxybenzeneꢀ1,3ꢀdiamine (16.6 mmol, 1.0 eq.) and Et3N (2.8 mL, 19.9 mmol, 1.2 eq.) in DCM (20mL) was added acetyl chloꢀ
ride (3.0 mL, 19.9 mmol, 1.2 eq.) in a dropwise manner under 0 oC, and the mixture was stirred at room temperature for 3 h. After
the reaction mixture was concentrated under reduced pressure, the residue was quenched with AcOEt and washed with saturated
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NaCl solution. After the organic layer was dried over Na2SO4, the solvent was removed to give a residue. To a solution of the resiꢀ
due (16.6 mmol, 1.0 eq.) in DMF (20 mL) was added NaH (60% dispersion in mineral oil, 0.80 g, 20 mmol), and the mixture was
stirred for 1h at room temperature. To the mixture was added 2ꢀ(chloromethyl)ꢀ1,4ꢀdimethoxybenzene and stirred for 5h at room
temperature. The mixture was poured into ice water and extracted with AcOEt three times. The combined organic layer was washed
with saturated NaCl solution. After the organic layer was dried over Na2SO4, the solvent was removed to give a residue. This resiꢀ
due (16.6 mmol, 1.0 eq.) was dissolved in Et2O/DCM (30/5 mL). MeOTf (2.4 mL, 21.6 mmol, 1.3 equiv) was added dropwise at
0 °C. After complete addition the reaction mixture was stirred for an additional 30 minutes at 0 °C. The solution was concentrated
and washed with Et2O (2 x 20 mL). The resulting compounds purified by column chromatography on silica gel (DCM: MeOH = 20 :
1). to give 9 (6.9 g, 71%) as white solid：1H NMR (400 MHz, DMSO) δ 7.99 (d, J = 3.2 Hz, 1H), 7.79 (dd, J = 9.3, 2.4 Hz, 1H),
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7.45 (t, J = 8.0 Hz, 2H), 7.26 (t, J = 7.4 Hz, 1H), 6.98 – 6.88 (m, 4H), 6.79 (dd, J = 10.9, 5.8 Hz, 2H), 4.84 (s, 2H), 3.59 (s, 3H),
3.53 (s, 9H), 3.50 (s, 3H), 1.91 (s, 3H); 13C{1H} NMR (101 MHz, DMSO) δ 169.4, 155.4, 154.2, 152.9, 151.2, 141.4, 132.8, 130.4,
125.6, 125.1, 123.7, 121.2, 119.5, 119.5, 117.0, 116.6, 112.1, 56.5, 55.7, 55.3, 45.6, 22.1.
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1,1-Dimethylindolin-1-ium trifluoromethanesulfonate (12a). A white solid (0.8 g, 54%). H NMR (400 MHz, DMSO) δ 7.84
(dd, J = 7.7, 4.2 Hz, 1H), 7.60 – 7.49 (m, 3H), 4.16 (t, J = 7.2 Hz, 2H), 3.49 (s, 9H), 3.38 (t, J = 7.2 Hz, 2H); 13C{1H} NMR (101
MHz, DMSO) δ 133.7, 130.7, 128.8, 126.5, 117.3, 67.4, 54.0, 26.6. HRMS m/z (ESI) calcd for C10H14N (M ꢀ OTf)+ 148.1121,
found 148.1120.
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1,1-Dimethyl-1,2,3,4-tetrahydroquinolin-1-ium trifluoromethanesulfonate (12b). A white solid (0.9 g, 58%). H NMR (400
MHz, DMSO) δ 8.03 – 7.93 (m, 1H), 7.50 – 7.41 (m, 2H), 7.38 (dd, J = 5.9, 3.4 Hz, 1H), 4.01 – 3.80 (m, 2H), 3.58 (s, 6H), 2.94 (t,
J = 5.9 Hz, 2H), 2.29 – 2.16 (m, 2H); 13C{1H} NMR (101 MHz, DMSO) δ 142.8, 131.0, 130.7, 129.6, 128.0, 121.3, 63.7, 56.7, 25.4,
16.8. HRMS m/z (ESI) calcd for C11H16N (M ꢀ OTf)+ 162.1277, found 162.1277.
1-Cyclopropyl-N,N,N-trimethyl-1-phenylmethanaminium trifluoromethanesulfonate (14). A white solid (0.6 g, 35%). 1H NMR
(400 MHz, DMSO) δ 7.55 (s, 2H), 7.52 – 7.48 (m, 3H), 3.94 (d, J = 10.8 Hz, 1H), 3.04 (s, 9H), 1.97 – 1.78 (m, 1H), 1.08 – 0.94 (m,
1H), 0.83 (td, J = 10.6, 5.0 Hz, 1H), 0.66 – 0.51 (m, 1H), ꢀ0.08 (qd, J = 9.6, 4.8 Hz, 1H); 13C{1H} NMR (101 MHz, DMSO) δ 133.1,
129.8, 128.7, 80.8, 51.0, 10.0, 3.3. HRMS m/z (ESI) calcd for C13H20N (M ꢀ OTf)+ 190.1590, found 190.1591.
General Procedure for Cleavage of the C-N Bonds.
The 25 mL Schlenk tube was added 4ꢀmethoxyꢀN,N,Nꢀtrimethyl ꢀbenzenaminium trifluoromethanesulfonate 1a (63.6 mg, 0.2
mmol), bis(pinacolato)diboron (127.0 mg, 0.5 mmol), Ni(COD)2 (3.3 mg, 6 mol %), ICy•HCl (6.5 mg, 12 mol %), KOtBu (44.9 mg,
200 mol%) ,toluene (0.5 mL) and 2ꢀethoxyethano (0.5 mL) under argon. The formed mixture was stirred at 50 ºC under Ar for 24 h
as monitored by TLC. The solution was then cooled to room temperature, and the solvent was removed under vaccum directly. The
crude product was purified by column chromatography on silica gel (Ethyl acetate: Petroleum ether = 1 : 100).
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2-(4-Methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4aa)27. A colorless oil (44.0 mg, 94%). H NMR (400 MHz,
CDCl3) δ 7.75 (d, J = 8.7 Hz, 2H), 6.90 (d, J = 8.7 Hz, 2H), 3.83 (s, 3H), 1.33 (s, 12H). 13C{1H} NMR (101 MHz, CDCl3) δ 136.5,
113.3, 83.54, 55.1, 24.9; ATRꢀFTIR (cmꢀ1): 2965, 2931, 1513, 1466, 1367, 1122, 1051, 884, 807, 746; GCꢀMS (EI) Calcd. for
C13H19BO3 [M] 234.14, found 234.21.
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4,4,5,5-Tetramethyl-2-phenyl-1,3,2-dioxaborolane (4ba)27. A colorless oil (28.9 mg, 71%). 1H NMR (400 MHz, CDCl3) δ 7.81
(dd, J = 7.9, 1.2 Hz, 2H), 7.48 – 7.44 (m, 1H), 7.39 – 7.35 (m, 2H), 1.35 (s, 12H);. 13C{1H} NMR (101 MHz, CDCl3) δ 134.7, 131.2,
127.7, 83.8, 24.9; ATRꢀFTIR (cmꢀ1): 2979, 2926, 2855, 2363, 1605, 1359, 1145, 1092, 1026, 963, 858, 700, 656; GCꢀMS (EI)
Calcd. for C12H17BO2 [M] 204.13, found 204.20.
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4,4,5,5-Tetramethyl-2-(o-tolyl)-1,3,2-dioxaborolane (4ca)28. A colorless oil (39.2 mg, 90 %). 1H NMR (400 MHz, CDCl3) δ 7.80
– 7.77 (m, 1H), 7.36 – 7.31 (m, 1H), 7.20 – 7.16 (m, 2H), 2.56 (s, 3H), 1.36 (s, 12H); 13C{1H} NMR (101 MHz, CDCl3) δ 144.8,
135.8, 130.8, 129.7, 124.7, 83.4, 24.9, 22.2; ATRꢀFTIR (cmꢀ1): 2979, 2927, 1601, 1442, 1379, 1348, 1312, 1269, 1146, 1042, 861,
761, 730, 662; GCꢀMS (EI) Calcd. for C13H19BO2 [M] 218.15, found 218.16.
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2-(3,4-Dimethylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4da)29 . A colorless oil (30.1 mg, 82%). H NMR (400 MHz,
CDCl3) δ 7.60 (s, 1H), 7.56 (d, J = 7.5 Hz, 1H), 7.16 (d, J = 7.4 Hz, 1H), 2.29 (s, 3H), 2.28 (s, 3H), 1.35 (s, 12H); 13C{1H} NMR
(101 MHz, CDCl3) δ 140.1, 135.9, 132.4, 129.1, 83.6, 24.8, 20.0, 19.4; ATRꢀFTIR (cmꢀ1): 2965, 2933, 2872, 1513, 1466, 1384,
1364, 1262, 1125, 1052, 886, 812, 739; GCꢀMS (EI) Calcd. for C14H21BO2 [M] 232.16, found 232.22.
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2-Mesityl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4ea)28. A colorless oil (40.1 mg (81%). H NMR (400 MHz, CDCl3) δ 6.79
(s, 2H), 2.39 (s, 6H), 2.26 (s, 3H), 1.39 (s, 13H); 13C{1H} NMR (101 MHz, CDCl3) δ 142.2, 138.9, 127.5, 83.5, 25.0, 22.2, 21.3;
ATRꢀFTIR (cmꢀ1): 2978, 2924, 1610, 1439, 1371, 1333, 1300, 1145, 1067, 855, 672; HRMS m/z (ESI) calcd for C15H24BO2 (M +
H)+ 247.1864, found 247.1867.
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2-(3-(Tert-butyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4fa)30 . A white solid (37.7 mg, 73%): H NMR (400 MHz,
CDCl3) δ 7.86 (s, 1H), 7.66 (d, J = 7.2 Hz, 1H), 7.52 (ddd, J = 7.9, 2.0, 1.3 Hz, 1H), 7.33 (t, J = 7.6 Hz, 1H), 1.36 (s, 21H); 13C{1H}
NMR (101 MHz, CDCl3) δ 150.2, 132.0, 131.4, 128.4, 127.5, 83.6, 34.6, 31.4, 24.9; ATRꢀFTIR (cmꢀ1): 3065, 2975, 2930, 1607,
1398, 1364, 1323, 1266, 1144, 1090, 859, 744, 660; GCꢀMS (EI) calcd for C16H25BO2 [M] 260.19, found 260.30.
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2-(2-(Benzyloxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4ga). A white solid (34.3 mg, 55%). H NMR (400 MHz,
CDCl3) δ 7.72 (dd, J = 7.3, 1.7 Hz, 1H), 7.63 (d, J = 7.3 Hz, 2H), 7.44 – 7.35 (m, 3H), 7.31 (d, J = 7.2 Hz, 1H), 7.04 – 6.91 (m, 2H),
5.14 (s, 2H), 1.38 (s, 13H); 13C{1H} NMR (101 MHz, CDCl3) δ 163.2, 137.6, 136.7, 132.5, 128.1, 127.3, 126.7, 120.6, 112.0, 83.4,
69.9, 24.9; ATRꢀFTIR (cmꢀ1): 2977, 2925, 2888, 2853, 1598, 1443, 1355, 1320, 1141, 1072, 861, 761, 744, 656; HRMS m/z (ESI)
calcd for C19H24BO3 (M + H)+ 311.1813, found 311.1821.
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2-(3-(Methoxymethoxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4ha). A white solid (42.3 mg, 80%): H NMR (300
MHz, CDCl3) δ 7.50 – 7.42 (m, 2H), 7.34 – 7.27 (m, 1H), 7.13 (ddd, J = 8.2, 2.6, 1.2 Hz, 1H), 5.20 (s, 2H), 3.48 (s, 3H), 1.34 (s,
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12H); 13C{1H} NMR (101 MHz, CDCl3) δ 156.6, 128.9, 128.3, 121.8, 119.5, 94.3, 83.8, 55.9, 24.9; ATRꢀFTIR (cmꢀ1): 2979, 1577,
1431, 1354, 1317, 1148, 1077, 1016, 707; HRMS m/z (ESI) calcd for C14H22BO4 (M + H)+ 265.1606, found 265.1607.
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4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)phenol (4ia)31 . A white solid (21.4 mg, 48 %): H NMR (400 MHz, CDCl3) δ
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7.70 (d, J = 8.5 Hz, 2H), 6.86 – 6.78 (m, 2H), 5.43 (s, 1H), 1.33 (s, 12H); 13C{1H} NMR (101 MHz, CDCl3) δ 158.4, 136.8, 114.8,
83.7, 24.8；ATRꢀFTIR (cmꢀ1): 3175, 2978, 2925, 2854, 1657, 1607, 1358, 1268, 1142, 1087, 838, 655; GCꢀMS (EI) calcd for
C12H17BO3 [M] 220.13, found 220.22.
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1-(5-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)indolin-1-yl)ethan-1-one (4ja)32. A white solid (48.0 mg, 84 %): H NMR
(400 MHz, CDCl3) δ 8.18 (d, J = 8.1 Hz, 1H), 7.66 (d, J = 8.1 Hz, 1H), 7.62 (s, 1H), 4.04 (t, J = 8.5 Hz, 2H), 3.17 (t, J = 8.5 Hz,
2H), 2.22 (s, 3H), 1.33 (s, 12H); 13C{1H} NMR (101 MHz, CDCl3) δ 168.9, 145.4, 134.9, 130.6, 130.3, 116.2, 83.6, 48.9, 27.6, 24.9,
24.6; ATRꢀFTIR (cmꢀ1): 2973, 2926, 1657, 1605, 1438, 1355, 1151, 907, 735, 668; HRMS m/z (ESI) calcd for C16H23BNO3 (M +
H)+ 288.1766, found 288.1768.
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t-Butyl (4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)carbamate (4ka)27. A white solid (54.2 mg, 85 %): H NMR
(400 MHz, CDCl3) δ 7.77 – 7.68 (m, 2H), 7.36 (d, J = 8.4 Hz, 2H), 6.67 (s, 1H), 1.50 (s, 9H), 1.32 (s, 12H); 13C{1H} NMR (101
MHz, CDCl3) δ 152.5, 141.1, 135.8, 117.2, 83.7, 28.3, 24.9；ATRꢀFTIR (cmꢀ1): 3333, 2978, 2931, 1732, 1609, 1587, 1529, 1506,
1398, 1362, 1317, 1231, 1145, 1091, 837, 656. HRMS m/z (ESI) calcd for C17H26BNO4Na (M + Na)+ 342.1847, found 342.1853.
4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (4la)31. A white solid (26.8 mg, 62 %). 1H NMR (400 MHz, CDCl3) δ
7.62 (d, J = 8.4 Hz, 2H), 6.66 (d, J = 8.4 Hz, 2H), 1.32 (s, 12H); 13C{1H} NMR (101 MHz, CDCl3) δ 149.3, 136.4, 114.1, 83.3,
24.8; ATRꢀFTIR (cmꢀ1): 2973, 2922, 1604, 1357, 1317, 1270, 1141, 1092, 858, 815, 738, 656. HRMS m/z (ESI) calcd for
C12H18BNO2Na (M + Na)+ 242.1323, found 242.1329.
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2-(4-Fluorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4ma)27. A colorless oil (22.6 mg, 51 %). H NMR (400 MHz,
CDCl3) δ 7.79 (dd, J = 8.5, 6.3 Hz, 2H), 7.10 – 6.99 (m, 2H), 1.34 (s, 12H); 13C{1H} NMR (101 MHz, CDCl3) δ 166.3, 163.8, 137.0,
114.9, 114.7, 83.9, 24.8; ATRꢀFTIR (cmꢀ1): 2976, 2923, 2853, 2364, 1633, 1365, 1145, 802, 523; GCꢀMS (EI) calcd for
C12H16BFO2 [M] 222.12, found 222.16.
N-Methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide (4na). A white solid (33.2 mg, 63 %). 1H NMR (400 MHz,
CDCl3) δ 7.85 (d, J = 8.2 Hz, 2H), 7.74 (d, J = 8.2 Hz, 2H), 6.22 (s, 1H), 3.01 (d, J = 4.9 Hz, 3H), 1.35 (s, 12H). 13C{1H} NMR
(101 MHz, CDCl3) δ 168.1, 136.8, 134.9, 125.9, 84.1, 26.8, 24.9; ATRꢀFTIR (cmꢀ1): 2978, 2929, 2363, 1644, 1550, 1397, 1361,
1326, 1144, 1098, 857, 658; HRMS m/z (ESI) calcd for C14H21BNO3 (M + H)+ 262.1609, found 262.1617.
3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoic acid (4oa). A white solid (26.3 mg, 53 %). 1H NMR (400 MHz, CDCl3)
δ 8.57 (s, 1H), 8.20 (dd, J = 6.4, 1.4 Hz, 1H), 8.04 (d, J = 7.4 Hz, 1H), 7.49 (t, J = 7.6 Hz, 1H), 1.37 (s, 12H); 13C{1H} NMR (101
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MHz, CDCl3) δ 171.8, 140.0, 136.6, 132.8, 128.7, 127.9, 84.2, 24.9; ATRꢀFTIR (cmꢀ1): 2978, 2638, 2361, 1682, 1605, 1406, 1387,
1357, 1326, 1292, 1077, 961, 848, 761; HRMS m/z (ESI) calcd for C13H17BO4Na (M + Na)+ 271.1112, found 271.1120.
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2-(Dibenzo[b,d]furan-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4pa). A white solid (50.3 mg, 85%). H NMR (400 MHz,
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7.31 (m, 1H), 1.40 (s, 12H); 13C{1H} NMR (101 MHz, CDCl3) δ 156.6, 155.9, 128.9, 127.7, 126.8, 124.1, 122.6, 121.0, 120.0,
117.6, 111.8, 84.0 , 25.0; ATRꢀFTIR (cmꢀ1): 2978, 2926, 1633, 1501, 1355, 1326, 1189, 1067, 964, 910, 827, 795, 727, 686; HRMS
m/z (ESI) calcd for C18H20BO3 (M + H)+ 295.1500, found 295.1506.
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9-Ethyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (4qa). A white solid (60.4 mg, 93%). 1H NMR (400 MHz,
CDCl3) δ 8.62 (s, 1H), 8.14 (d, J = 7.7 Hz, 1H), 7.94 (dd, J = 8.2, 1.0 Hz, 1H), 7.49 – 7.42 (m, 1H), 7.38 (dd, J = 8.2, 4.8 Hz, 2H),
7.27 – 7.20 (m, 1H), 4.33 (q, J = 7.2 Hz, 2H), 1.42 – 1.36 (m, 15H); 13C{1H} NMR (101 MHz, CDCl3) δ 142.0, 140.0, 132.1, 127.8,
125.58, 123.1, 122.6, 120.6, 119.2, 108.4, 107.8, 83.5, 37.5, 24.9, 13.7; ATRꢀFTIR (cmꢀ1): 2977, 2931, 1595, 1476, 1429, 1351,
1326, 1301, 1264, 1231, 1143, 1231, 1077, 962, 810, 748, 627; HRMS m/z (ESI) calcd for C20H25BNO2 (M + H)+ 322.1973, found
322.1979.
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Isopentyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate (4ra). A colorless oil (41.7 mg, 66%). H NMR (400 MHz,
CDCl3) δ 8.04–7.97 (m, 2H), 7.86 (d, J = 8.3 Hz, 2H), 4.35 (t, J = 6.8 Hz, 2H), 1.85–1.73 (m, 1H), 1.68 (t, J = 6.8 Hz, 2H), 1.35
(s, 12H), 0.98 (s, 3H), 0.96 (s, 3H)；13C{1H} NMR (101 MHz, CDCl3): δ 166.7, 134.6, 132.7, 128.5, 84.1, 63.7, 37.4, 25.2, 24.8,
22.5; ATRꢀFTIR (cmꢀ1): 2960, 1722, 1399, 1362, 1269, 1145, 1113, 858, 710, 651; HRMS m/z (ESI) calcd for C18H28BO4(M + H)+
319.2075, found 319.2080.
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3-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl dimethylcarbamate (4sa)33. A white solid (23.4 mg, 42%). H NMR
(400 MHz, CDCl3) δ 7.65 – 7.59 (m, 1H), 7.53 (d, J = 1.9 Hz, 1H), 7.36 (t, J = 7.7 Hz, 1H), 7.21 (ddd, J = 8.1, 2.5, 1.1 Hz, 1H),
3.08 (s, 3H), 3.00 (s, 3H), 1.33 (s, 12H); 13C{1H} NMR (101 MHz, CDCl3) δ 155.0, 151.1, 131.5, 128.7, 127.7, 124.8, 83.9, 36.7,
36.4, 24.8; ATRꢀFTIR (cmꢀ1): 2927, 1724, 1611, 1499, 1442, 1385, 1353, 1206, 1168, 849; HRMS m/z (ESI) calcd for C15H23BNO4
(M + H)+ 292.1715, found 292.1718.
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1-Phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)diazene (4ta)31. A yellow solid (24.6 mg, 40%). H NMR
(400 MHz, CDCl3) δ 7.68 (d, J = 8.5 Hz, 2H), 7.24 – 7.17 (m, 2H), 6.88 – 6.78 (m, 5H), 1.32 (s, 12H)；13C{1H} NMR (101
MHz, CDCl3) δ 151.5, 148.5, 136.4 129.4, 120.1, 112.4, 111.3, 83.4, 24.9; ATRꢀFTIR (cmꢀ1): 2977, 2925, 2261, 1604, 1395, 1358,
1271, 1143, 1087, 856, 766, 689, 654; HRMS m/z (ESI) calcd for C18H22BN2O2 (M + H)+ 309.1769, found 309.1777.
Bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)methane (4ua)34. A white solid (60.1 mg, 72%): 1H NMR (400 MHz,
CDCl3) δ 7.75 (d, J = 8.0 Hz, 2H), 7.20 (d, J = 8.0 Hz, 2H), 4.02 (s, 1H), 1.34 (s, 12H); 13C{1H} NMR (101 MHz, CDCl3) δ 144.1,
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135.0, 128.4, 83.6, 42.3, 24.8; ATRꢀFTIR (cmꢀ1): 2979, 2927, 1608, 1515, 1464, 1399, 1360, 1322, 1269, 1143, 1089, 1019, 963,
858, 736, 660; GCꢀMS (EI) calcd for C25H34B2O4 [M] 420.26, found 420.40.
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2,2'-(Oxybis(4,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (4va) . A white solid (70.3 mg, 83%). H NMR (400
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83.8, 24.8; ATRꢀFTIR (cmꢀ1): 2898, 2922, 1638, 1478, 1367, 1343, 1138, 1278, 1015, 947; HRMS m/z (ESI) calcd for C24H33B2O5
(M + H)+ C25H34B2O4 [M] 423.2509, found 423.2513.
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2,2'-((Phenylmethylene)bis(4,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (4wa) . A white solid (94.2 mg, 95%).
1H NMR (400 MHz, CDCl3) δ 7.73 (d, J = 8.0 Hz, 4H), 7.93 (dd, J = 5.9, 1.5 Hz, 1H), 7.27ꢀ7.07 (m, 9H), 5.56 (s, 1H), 1.32 (s, 1H);
13C{1H} NMR (101 MHz, CDCl3) δ 146.9, 143.4, 134.8, 129.4, 128.9, 128.3, 126.3, 83.6, 57.1, 24.8; ATRꢀFTIR (cmꢀ1): 2978, 2362,
1608, 1399, 1361, 1323, 1271, 1144, 1089, 1021, 962, 858, 701. HRMS m/z (ESI) calcd for C31H39B2O4 (M + H)+ 497.3029, found
497.3035.
2,2'-((9H-Fluorene-9,9-diyl)bis(4,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4xa) . A white solid (107.2 mg,
94%). 1H NMR (400 MHz, CDCl3) δ 7.75 (d, J = 7.5 Hz, 1H), 7.67 (d, J = 8.2 Hz, 2H), 7.34 (dd, J = 13.1, 7.5 Hz, 2H), 7.22 (ddd, J
= 16.8, 9.2, 4.5 Hz, 3H), 1.29 (s, 12H); 13C{1H} NMR (151 MHz, CDCl3) δ 150.7, 149.0, 140.2, 134.7, 127.8, 127.5, 126.1, 120.1,
83.66, 65.9, 24.8; ATRꢀFTIR (cmꢀ1): 2977, 2930, 1607, 1515, 1447, 1361, 1269, 1214, 1144, 1090, 1018, 982, 962, 919, 856, 819,
746, 660, 520, 443. HRMS m/z (ESI) calcd for C37H42B2O4 (M + H)+ 571.3185, found 571.3188.
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2-(4-Methoxyphenyl)-5,5-dimethyl-1,3,2-dioxaborinane (4ab)35. A white solid (32.3 mg, 73%): H NMR (400 MHz, CDCl3) δ
7.81 – 7.70 (m, 2H), 6.94 – 6.86 (m, 2H), 3.83 (s, 3H), 3.76 (s, 4H), 1.02 (s, 6H); 13C{1H} NMR (101 MHz, CDCl3) δ 161.7, 135.5,
113.1, 72.2, 55.0, 31.9, 21.9; ATRꢀFTIR (cmꢀ1): 2961, 2838, 1603, 1478, 1420, 1318, 1247, 1176, 1134, 1105, 1031, 834, 647;
HRMS m/z (ESI) calcd for C12H18BO3 (M + H)+ 221.1344, found 221.1338.
2-(4-Methoxyphenyl)-4,4,6-trimethyl-1,3,2-dioxaborinane (4ac)36. A colorless oil (43.1 mg, 92%). 1H NMR (400 MHz, CDCl3)
δ 7.77 (d, J = 8.6 Hz, 2H), 6.88 (d, J = 8.7 Hz, 2H), 4.33 (dqd, J = 12.3, 6.2, 3.0 Hz, 1H), 3.82 (s, 3H), 1.85 (dd, J = 13.9, 2.9 Hz,
1H), 1.60 (dd, J = 15.0, 3.2 Hz, 1H), 1.36 (dd, J = 9.7, 5.6 Hz, 9H); 13C{1H} NMR (101 MHz, CDCl3) δ 161.5, 135.4, 113.0, 70.8,
64.8, 55.0, 46.0, 31.3, 28.1, 23.2; ATRꢀFTIR (cmꢀ1): 2974, 2935, 1603, 1511, 1411, 1384, 1359, 1330, 1305, 1245, 1208, 1168,
1107, 1032, 834, 805, 768, 649; HRMS m/z (ESI) calcd for C13H20BO3 (M + H)+ 235.1500, found 235.1500.
2-Benzyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7aa)37. The reaction of 6a (59.8 mg, 0.20 mmol), (Bpin)2 (127.0 mg, 0.50
mmol), Ni(COD)2 (3.3 mg, 6 mol %), ICy HCl (6.5 mg, 12 mol %) and NaOtBu (38.4 mg, 200 mol%) in toluene/2ꢀethoxyethano
(0.5/0.5 mL) at 50 ºC under Ar after column chromatography on silica (Ethyl acetate: Petroleum ether = 1 : 100) to afford 33.1 mg
(76%) of 7aa as colorless oil: 1H NMR (400 MHz, CDCl3) δ 7.23 (dd, J = 9.9, 4.7 Hz, 2H), 7.18 (d, J = 6.7 Hz, 2H), 7.11 (t, J = 7.1
Hz, 1H), 2.29 (s, 2H), 1.23 (s, 12H); 13C{1H} NMR (101 MHz, CDCl3) δ 138.7, 129.0, 128.3, 124.8, 83.4, 24.7; ATRꢀFTIR (cmꢀ1):
2966, 2934, 1494, 1466, 1452, 1385, 1367, 1120, 1051, 882, 727, 700; GCꢀMS (EI) calcd for C13H19BO2 [M] 218.15, found 218.15.
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4,4,5,5-Tetramethyl-2-(3-methylbenzyl)-1,3,2-dioxaborolane (7ba)38. A colorless oil (33.6 mg, 71%). 1H NMR (400 MHz,
CDCl3) δ 7.14 (t, J = 7.5 Hz, 1H), 6.99 (d, J = 7.7 Hz, 2H), 6.94 (d, J = 7.5 Hz, 1H), 2.31 (s, 3H), 2.26 (s, 2H), 1.24 (s, 12H);
13C{1H} NMR (101 MHz, CDCl3) δ 138.4, 137.7, 129.8, 128.1, 125.9, 125.6, 83.4, 24.7, 21.4; ATRꢀFTIR (cmꢀ1): 2979, 2926, 1607,
1451, 1333, 1272, 1145, 968, 877, 848, 781, 740, 701, 674; HRMS m/z (ESI) calcd for C14H22BO2 (M + H)+ 233.1707, found
233.1708.
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2-(2,3-Dimethylbenzyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7ca). A colorless oil (35.6 mg, 72%). H NMR (400 MHz,
CDCl3) δ 7.04 – 6.93 (m, 3H), 2.29 (d, J = 2.2 Hz, 2H), 2.29 (s, 3H), 2.18 (s, 3H), 1.24 (s, 12H); 13C{1H} NMR (101 MHz, CDCl3)
δ 137.4, 136.3, 134.4, 127.5, 127.0, 125.2, 83.3, 24.7, 20.7, 15.8; ATRꢀFTIR (cmꢀ1): 2978, 2927, 1488, 1330, 1144, 968, 847;
HRMS m/z (ESI) calcd for C15H24BO2 (M + H)+ 247.1864, found 247.1867.
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2-(2-Methoxybenzyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7da)38. A colorless oil (36.1 mg, 73%). H NMR (400 MHz,
CDCl3) δ 7.13 (dd, J = 11.6, 4.5 Hz, 2H), 6.84 (ddd, J = 16.7, 11.6, 4.7 Hz, 2H), 3.80 (s, 3H), 2.19 (s, 2H), 1.24 (s, 12H); 13C{1H}
NMR (101 MHz, CDCl3) δ 157.1, 130.4 127.9, 126.2 120.4, 109.7, 83.1, 55.0, 24.7; ATRꢀFTIR (cmꢀ1): 2978, 2932, 1601, 1492,
1464, 1353, 1328, 1244, 1144, 1030, 969, 849, 754, 674; HRMS m/z (ESI) calcd for C14H22BO3 (M + H)+ 249.1657, found
249.1661.
2-(2-Methoxybenzyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7ea). A colorless oil (48.8 mg, 88%). 1H NMR (400 MHz,
CDCl3) δ 6.80 – 6.65 (m, 3H), 3.84 (s, 3H), 3.83 (s, 3H), 2.22 (s, 2H), 1.23 (s, 12H); 13C{1H} NMR (101 MHz, CDCl3) δ 148.6,
146.4, 130.9 120.7, 112.4, 111.3, 83.3, 55.7, 24.7; ATRꢀFTIR (cmꢀ1): 2977, 2936, 2839, 1681, 1591, 1514, 1458, 1375, 1337, 1268,
1141, 1026, 860, 809, 763, 640; HRMS m/z (ESI) calcd for C15H24BO4 (M + H)+ 279.1762, found 279.1766.
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2-(Benzo[d][1,3]dioxol-5-ylmethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7fa). A colorless oil (47.3 mg, 90%). H NMR
(400 MHz, CDCl3) δ 6.72 – 6.66 (m, 2H), 6.61 (dd, J = 7.9, 1.6 Hz, 1H), 5.89 (s, 2H), 2.21 (s, 2H), 1.23 (s, 12H); 13C{1H} NMR
(101 MHz, CDCl3) δ 147.4, 144.9, 132.1, 121.4, 109.6, 108.1, 100.5, 83.4, 24.7; ATRꢀFTIR (cmꢀ1): 2979, 2930, 1722, 1689, 1606,
1447, 1376, 1252, 1148, 1099, 1039, 930, 851, 810, 674; HRMS m/z (ESI) calcd for C14H20BO4 (M + H)+ 263.1449, found
263.1450.
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2-(2,4-Difluorobenzyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7ga). A colorless oil (35.7 mg, 70%). H NMR (400 MHz,
CDCl3) δ 7.14 (dt, J = 14.9, 7.4 Hz, 1H), 6.80 – 6.70 (m, 2H), 2.20 (s, 2H), 1.24 (s, 12H); 13C{1H} NMR (101 MHz, CDCl3) δ
164.1, 159.7, 131.4 (dd, J = 9.2, 6.5 Hz), 121.6 (dd, J = 17.1, 3.7 Hz), 110.7 (dd, J = 20.8, 3.8 Hz), 103.6, 103.3, 103.1, 83.6, 24.6;
ATRꢀFTIR (cmꢀ1): 2980, 2929, 2234, 1601, 1504, 1353, 1273, 1212, 1143, 966, 848; HRMS m/z (ESI) calcd for C13H18BF2O2(M +
H)+ 255.1362, found 255.1368.
4,4,5,5-Tetramethyl-2-(naphthalen-1-ylmethyl)-1,3,2-dioxaborolane (7ha)37. A colorless oil (39.0 mg, 73%). H NMR (300
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MHz, CDCl3) δ 8.03 (dd, J = 8.0, 1.1 Hz, 1H), 7.84 (dd, J = 7.3, 2.1 Hz, 1H), 7.71 – 7.65 (m, 1H), 7.53 – 7.44 (m, 2H), 7.42 – 7.34
(m, 2H), 2.71 (s, 2H), 1.21 (s, 12H); 13C{1H} NMR (101 MHz, CDCl3) δ 135.6, 133.7, 132.4, 128.5, 126.4, 125.7, 125.3, 124.5,
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83.5, 24.6; ATRꢀFTIR (cmꢀ1): 3052, 2978, 2928, 1691, 1511, 1449, 1375, 1346, 1217, 1146, 1075, 1008, 885, 852, 799, 776, 673;
HRMS m/z (ESI) calcd for C17H22BO2 (M + H)+ 269.1707, found 269.1709.
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4,4,5,5-Tetramethyl-2-(1-phenylethyl)-1,3,2-dioxaborolane (7ia)39. A colorless oil (36.7 mg, 79%). 1H NMR (400 MHz, CDCl3)
δ 7.24 – 7.11 (m, 5H), 7.10 – 7.01 (m, 1H), 2.36 (q, J = 7.5 Hz, 1H), 1.26 (d, J = 7.5 Hz, 3H), 1.13 (d, J = 5.3 Hz, 12H); 13C{1H}
NMR (101 MHz, CDCl3) δ 144.9, 128.3, 127.8, 125.1, 83.3, 24.6, 17.0; ATRꢀFTIR (cmꢀ1): 2976, 2921, 2850, 2361, 2337, 1633,
1605, 1395, 1361, 1319, 1248, 1143, 1092, 1031, 801, 654; GCꢀMS (EI) calcd for C14H21BO3 [M] 232.16, found 232.19.
4,4,5,5-Tetramethyl-2-(1-(o-tolyl)ethyl)-1,3,2-dioxaborolane (7ja). A colorless oil (37.2 mg, 75%). 1H NMR (400 MHz, CDCl3)
δ 7.24 – 7.20 (m, 1H), 7.14 (dd, J = 13.3, 6.7 Hz, 2H), 7.06 (td, J = 7.4, 1.4 Hz, 1H), 2.60 (q, J = 7.5 Hz, 1H), 2.33 (s, 3H), 1.35 (dd,
J = 10.0, 4.4 Hz, 3H), 1.23 (d, J = 4.8 Hz, 12H); 13C{1H} NMR (101 MHz, CDCl3) δ 143.3, 135.6, 130.0, 127.1, 126.0, 125.0, 83.2,
24.6, 19.9, 16.3; ATRꢀFTIR (cmꢀ1): 2978, 2929, 1442, 1375, 1329, 1218, 1148, 1077, 982, 850, 760, 674; GCꢀMS (EI) calcd for
C15H23BO2 [M] 246.18, found 247.21.
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2-(1-(4-Methoxyphenyl)ethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7ka)39. A colorless oil (47.1 mg, 90%). H NMR (400
MHz, CDCl3) δ 7.18 – 7.11 (m, 2H), 6.86 – 6.79 (m, 2H), 3.78 (s, 3H), 2.38 (q, J = 7.5 Hz, 1H), 1.30 (d, J = 7.5 Hz, 3H), 1.21 (d, J
= 5.1 Hz, 12H); 13C{1H} NMR (101 MHz, CDCl3) δ 157.2, 137.0, 128.6, 113.7, 83.2, 55.1, 24.6, 17.3; ATRꢀFTIR (cmꢀ1): 2927,
2930, 1675, 1605, 1512, 1455, 1372, 1248, 1174, 1146, 1087, 1033, 832, 674; HRMS m/z (ESI) calcd for C15H24BO3 (M + H)+
263.1813, found 263.1817.
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2-(1-(4-Fluorophenyl)ethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7la)39. A colorless oil (38.3 mg, 76%). H NMR (400
MHz, CDCl3) δ 7.20 – 7.12 (m, 2H), 6.98 – 6.90 (m, 2H), 2.41 (q, J = 7.5 Hz, 1H), 1.31 (d, J = 7.5 Hz, 3H), 1.20 (d, J = 4.6 Hz,
12H); 13C{1H} NMR (101 MHz, CDCl3) δ 162.0, 159.6 140.5 (d, J = 3.1 Hz), 129.0 (d, J = 7.6 Hz), 115.0, 114.8, 83.3, 24.6, 17.2;
ATRꢀFTIR (cmꢀ1): 2978, 2929, 1604, 1510, 1445, 1376, 1267, 1224, 1147, 1084, 1011, 982, 837, 674; GCꢀMS (EI) calcd for
C14H20BFO2 [M] 250.15, found 251.2.
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4,4,5,5-Tetramethyl-2-(1-(naphthalen-1-yl)ethyl)-1,3,2-dioxaborolane (7ma)40. A colorless oil (41.3 mg, 73%). H NMR (400
MHz, CDCl3) δ 8.11 (d, J = 8.1 Hz, 1H), 7.84 (dd, J = 7.4, 2.0 Hz, 1H), 7.71 – 7.64 (m, 1H), 7.54 – 7.37 (m, 4H), 3.13 (q, J = 7.4
Hz, 1H), 1.51 (d, J = 7.5 Hz, 3H), 1.21 (d, J = 4.1 Hz, 12H); 13C{1H} NMR (101 MHz, CDCl3) δ 141.4, 133.9, 132.0, 128.7, 125.8,
125.3, 124.1, 83.4, 24.6, 16.4; ATRꢀFTIR (cmꢀ1): 3049, 2977, 2930, 2362, 1510, 1453, 1375, 1324, 1143, 851, 798, 777, 673;
HRMS m/z (ESI) calcd for C18H24BO2 (M + H)+ 283.1864, found 283.1867.
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4,4,5,5-Tetramethyl-2-(1,2,3,4-tetrahydronaphthalen-1-yl)-1,3,2-dioxaborolane (7na)39. A colorless oil (37.9 mg, 74%). H
NMR (400 MHz, CDCl3) δ 7.25ꢀ7.05 (m, 4H), 2.77 (s, 2H), 2.60 (s, 1H), 1.90 (s, 3H), 1.81 – 1.68 (m, 1H), 1.25 (s, 12H); 13C{1H}
NMR (101 MHz, CDCl3) δ 136.6, 135.6, 128.3, 124.3, 123.7, 82.2, 28.7, 24.1, 24.0, 21.6; ATRꢀFTIR (cmꢀ1): 2927, 2928, 1684,
1452, 1382, 1324, 1145, 852, 740, 672; HRMS m/z (ESI) calcd for C16H24BO2 (M + H)+ 259.1864, found 259.1869.
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4,4,5,5-Tetramethyl-2-(1-phenyl-2-(p-tolyl)ethyl)-1,3,2-dioxaborolane (7oa). A colorless oil (46.7 mg, 72%). H NMR (400
MHz, CDCl3) δ 7.26 – 7.21 (m, 4H), 7.16 – 7.09 (m, 1H), 7.04 (dd, J = 19.6, 8.0 Hz, 4H), 3.12 (dd, J = 13.5, 9.6 Hz, 1H), 2.91 (dd,
J = 13.5, 7.0 Hz, 1H), 2.65 (dd, J = 9.6, 7.0 Hz, 1H), 2.28 (s, 3H), 1.11 (d, J = 2.5 Hz, 12H); 13C{1H} NMR (101 MHz, CDCl3) δ
142.6, 138.6, 135.0, 128.7, 128.3, 125.3, 83.3, 38.3, 24.5, 21.0; ATRꢀFTIR (cmꢀ1): 2978, 2925, 1595, 1451, 1360, 1326, 1240, 1142,
1088, 967, 855, 700; HRMS m/z (ESI) calcd for C21H28BO2 (M + H)+ 322.2177, found 322.2179.
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Methyl 3-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propanoate (7pa)41. A colorless oil (18.2 mg, 31%). H NMR
(400 MHz, CDCl3) δ 7.30 – 7.19 (m, 5H), 7.19 – 7.12 (m, 1H), 3.65 (s, 3H), 2.90 (dd, J = 15.9, 9.8 Hz, 1H), 2.70 – 2.63 (m, 2H),
1.22 (s, 6H), 1.17 (s, 6H); 13C{1H} NMR (101 MHz, CDCl3) δ 173.8, 141.3, 128.5, 128.2, 125.7, 83.6, 51.6, 37.1, 24.5; ATRꢀFTIR
(cmꢀ1): 3061, 2977, 1736, 1637, 1371, 1324, 1261, 1171, 1140, 1050, 973, 846,766,701; HRMS m/z (ESI) calcd for C16H23BO4Na
(M + Na)+ 313.1582, found 313.1589.
4,4,5,5-Tetramethyl-2-(2-phenylpropan-2-yl)-1,3,2-dioxaborolane (7qa)37. A colorless oil (36.6 mg, 74%). 1H NMR (400 MHz,
CDCl3) δ 7.37 – 7.26 (m, 4H), 7.13 (ddd, J = 6.6, 3.2, 1.6 Hz, 1H), 1.35 (s, 6H), 1.20 (s, 12H); 13C{1H} NMR (101 MHz, CDCl3) δ
148.6, 128.1, 126.3, 125.0, 83.3, 25.6, 24.5; ATRꢀFTIR (cmꢀ1): 2872, 2802, 1432, 1344, 1208, 1192, 1054, 972, 838; HRMS m/z
(ESI) calcd for C15H24BO2 (M + H)+ 247.1864, found 247.1864.
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4,4,5,5-Tetramethyl-2-(1-phenylcyclopentyl)-1,3,2-dioxaborolane (7ra). A white solid (33.9 mg, 63%). H NMR (400 MHz,
CDCl3): δ 7.31 – 7.22 (m, 5H), 7.14 – 7.07 (m, 1H), 2.32 (d, J = 8.2 Hz, 2H), 1.78 – 1.59 (m, 6H), 1.13 (s, 12H); 13C{1H} NMR
(101 MHz, CDCl3): δ 147.1, 127.9, 127.0, 124.7, 83.3, 35.2, 24.4; ATRꢀFTIR (cmꢀ1): 2973, 2864, 1446, 1374, 1354, 1312, 1111,
748, 700; HRMS m/z (ESI) calcd for C17H26BO2 (M + H)+ 273.2020, found 273.2026.
4,4,5,5-tetramethyl-2-(1-phenylcyclopentyl)-1,3,2-dioxaborolane (7sa)42. A colorless oil (31.4 mg, 60%). H NMR (400 MHz,
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Hz, 12H), 1.09 (s, 3H), 0.82 (t, J = 7.4 Hz, 3H); 13C{1H} NMR (101 MHz, CDCl3): δ 147.2, 127.7, 126.9, 126.8, 125.0, 83.3, 31.9,
24.6, 21.0, 1.0; ATRꢀFTIR (cmꢀ1): 2965, 2925, 1637, 1461, 1372, 1349, 1313, 1261, 1142, 1097, 1026, 801, 700; HRMS m/z (ESI)
calcd for C12H26BO2 (M + H)+ 261.2020, found 261.2022.
4,4,5,5-Tetramethyl-2-(1-phenylcyclopropyl)-1,3,2-dioxaborolane (7ta)43. A colorless oil (24.2 mg, 50%). H NMR (400 MHz,
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(101 MHz, CDCl3) δ 144.8, 128.9, 128.0, 125.2, 83.3, 24.6, 13.3; ATRꢀFTIR (cmꢀ1): 2946, 2932, 1643, 1421, 1353, 1312, 1127,
838, 737, 655; HRMS m/z (ESI) calcd for C15H22BO2 (M + H)+ 244.1635, found 244.1640.
N-(2,5-Dimethoxybenzyl)-N-(2-phenoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)acetamide (10)44. A white solid
(90.2 mg, 84%). 1H NMR (400 MHz, CDCl3) δ 7.57 (dd, J = 7.0, 1.5 Hz, 2H), 7.31 (dd, J = 11.2, 4.7 Hz, 2H), 7.14 (t, J = 7.4 Hz,
1H), 6.99 (d, J = 3.0 Hz, 1H), 6.86 – 6.80 (m, 2H), 6.74 (d, J = 8.7 Hz, 1H), 6.68 (dt, J = 5.1, 2.5 Hz, 1H), 6.62 (d, J = 8.9 Hz, 1H),
4.98 (d, J = 12.0 Hz, 1H), 4.90 (d, J = 12.0 Hz, 1H), 3.63 (s, 3H), 3.50 (s, 3H), 1.97 (s, 3H), 1.32 (d, J = 4.7 Hz, 12H); 13C{1H}
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NMR (101 MHz, CDCl3) δ 171.1, 156.3, 155.3, 153.4, 151.8, 136.9, 135.5, 132.4, 129.8, 126.4, 124.3, 119.7, 116.7, 116.3, 113.6,
111.2, 83.9, 55.6, 46.4, 25.0, 24.6, 22.3; ATRꢀFTIR (cmꢀ1): 2979, 2834, 1663, 1588, 1498, 1422, 1384, 1357, 1245, 1222, 1142,
1048, 860, 753, 692.
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35%). H NMR (400 MHz, CDCl3) δ 7.86 (d, J = 6.9 Hz, 1H), 7.41 (t, J = 7.1 Hz, 1H), 7.28 (t, J = 6.9 Hz, 2H), 3.31 (dt, J = 8.9,
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5.5 Hz, 2H), 3.23 (dt, J = 8.3, 5.4 Hz, 2H), 2.96 (s, 6H), 1.36 (s, 12H); 13C{1H} NMR (101 MHz, CDCl3) δ 141.8, 137.1, 132.0,
130.2, 126.8, 84.0, 60.3, 43.6, 30.9, 24.9; ATRꢀFTIR (cmꢀ1): 3057, 2980, 2938, 2862, 1447, 1380, 1349, 1278, 1163, 1031, 857,
749, 640, 519; GCꢀMS (EI) calcd for C16H26BNO2 [M] 275.21, found 275.30.
N,N-Dimethyl-3-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)propan-1-amine (13ba). A colorless oil (24.5 mg,
42%). 1H NMR (400 MHz, CDCl3) δ 7.81 (dd, J = 7.4, 1.3 Hz, 1H), 7.36 (td, J = 7.5, 1.5 Hz, 1H), 7.23 – 7.15 (m, 2H), 2.97 – 2.84
(m, 4H), 2.71 (s, 6H), 2.05 – 1.88 (m, 2H), 1.33 (s, 12H); 13C{1H} NMR (101 MHz, CDCl3) δ 147.1, 136.6, 131.3, 129.2, 125.7,
83.6, 58.5, 43.8, 32.5, 28.0, 24.8; ATRꢀFTIR (cmꢀ1): 2978, 2931, 2363, 1600, 1443, 1381, 1348, 1276, 1147, 1030, 860, 639; GCꢀ
MS (EI) calcd for C17H28BNO2 [M] 289.22, found 289.32.
1
2-(Cyclopropyl(phenyl)methyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (15). A colorless oil (28.8 mg, 55%). H NMR (400
MHz, CDCl3) δ 7.28 – 7.23 (m, 3H), 7.23 – 7.11 (m, 2H), 1.72 (d, J = 9.7 Hz, 1H), 1.22 (d, J = 1.4 Hz, 12H), 1.17 – 1.14 (m, 1H),
0.61 – 0.52 (m, 1H), 0.52 – 0.43 (m, 1H), 0.25 (td, J = 9.3, 5.1 Hz, 1H), 0.09 (td, J = 9.4, 5.1 Hz, 1H); 13C{1H} NMR (101 MHz,
CDCl3) δ 143.1, 128.2, 125.2, 83.3, 24.6, 13.0, 5.0, 4.7; ATRꢀFTIR (cmꢀ1): 2979, 2929, 2362, 1455, 1374, 1324, 1144, 971, 850,
700, 673; HRMS m/z (ESI) calcd for C16H24BO2 (M + H)+ 258.1791, found 258.1794.
■ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.joc.xxxxxxx
NMR spectra of all compounds (PDF)
■AUTHOR INFORMATION
Corresponding Authors
shiz@nju.edu.cn
Notes
The authors declare no competing financial interest.
■ACKNOWLEDGMENTS
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We thank the “1000ꢀYouth Talents Plan”, the “Jiangsu SpeciallyꢀAppointed Professor Plan”, NSF of China (Grant 21402086), and NSF of
Jiangsu Province (Grant BK20140594) for financial support. This work was also supported by a Project Funded by the Priority Academic
Program Development of Jiangsu Higher Education Institutions. We also thank Chendan Zhu in our group for reproducing the results of
4ja and 7oa in Table 2 and 3.
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