Cu-Catalyzed asymmetric hydroboration of naphthylallylic compounds for enantioselective synthesis of chiral boronates

Article abstract of DOI:10.1021/acs.joc.9b00289

A Cu-catalyzed regio- A nd enantioselective hydroboration of various naphthylallylic compounds affording chiral boronates with high yields and excellent enantioselectivities (up to 96% ee) was presented. The utility of the boronated products is further illustrated by other stereospecific C-B bond transformations to produce amino alcohols and other useful compounds.

Full text of DOI:10.1021/acs.joc.9b00289

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Article
Cu-Catalyzed Asymmetric Hydroboration of Naphthylallylic
Compounds for Enantioselective Synthesis of Chiral Boronates
Suna Han, Xin Shen, Duanyang Kong, Guofu Zi, Guohua Hou, and Jiaxin Zhang
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b00289 • Publication Date (Web): 19 Mar 2019
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Cu-Catalyzed Asymmetric Hydroboration of Naphthylallylic Compounds for
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Enantioselective Synthesis of Chiral Boronates
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Suna Han, Xin Shen, Duanyang Kong, Guofu Zi, Guohua Hou*, and Jiaxin Zhang*
Key Laboratory of Radiopharmaceuticals, College of Chemistry, Beijing Normal University,
Beijing 100875, China
E-mail: ghhou@bnu.edu.cn; zhangjiaxin@bnu.edu.cn
ABSTRACT:
A Cu-catalyzed regio- and enantioselective hydroboration of various
naphthylallylic compounds affording chiral boronates with high yields and excellent
enantioselectivities (up to 96% ee) was presented. The utility of the boronated products is further
illustrated by other stereospecific C-B bond transformations to produce amino alcohols and other
useful compounds.
INTRODUCTION
Chiral organoboronates play an important role in synthetic chemistry, material science,
chemical biology, and are key intermediates in the synthesis of many pharmaceuticals or
agrochemicals.1 Therefore, the synthesis of chiral organoboron compounds has attracted great
interest from chemists. Metal-catalyzed enantioselective construction of C−B bond has received
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much attention as the resulting boronated products are versatile intermediates, which can be easily
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transformed into C-O, C-N, C-C, and C-halogen bonds.2 Over the past few decades, there are
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many metal precursors employed in asymmetric hydroboration, such as Rh, 3 Ir, 4 Pd, 5 Co and
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Cu.7 Amongst the reported methods, copper-catalyzed hydroboration has received considerable
attention due to the commercial availability, low cost and stability of copper metal. Yun and
co-workers reported copper-catalyzed asymmetric hydroboration of styrenes, borylalkenes and
bicyclic alkenes with high enantioselectivities using diphosphine ligands, Tangphos,
DTBM-Segphos, and Taniaphos, respectively.8 Hoveyda group developed highly enantioselective
hydroboration of 1, 2-disubstituted and 1, 1-disubstituted aryl alkenes catalyzed by Cu-based
bidentate N-heterocyclic carbene complexes.9 Hartwig group successfully applied aliphatic
internal alkenes to the copper catalyzed asymmetric hydroboration achieving high regio- and
enantioselectivities.10 Besides, Ito, Lin and Tortosa groups independently developed the methods
to stereoselective synthesis of cycloalkanes via Cu-catalyzed asymmetric hydroboration. It was
demonstrated that the copper catalyzed asymmetric hydroboration of cycloalkenes,11 allylic
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carbonates
and phosphates,13 and homoallylic sulfonates
was an efficient approach for
synthesis of chiral cycloalkanes. Various α, β-unsaturated compounds including α, β-unsaturated
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carbonyl compounds,7a, 7g, 15 α, β-unsaturated nitriles,7a, 15b phosphonates
and sulfones,17 and
other α, β unsaturated functional compounds,8b, 18 were also explored in the copper-catalyzed
asymmetric hydroboration by many research groups achieving high yields and enantioselectivities.
To the hydroboration of N-hetero cyclic substrates, Ito and co-workers made important
contribution and reported Cu-catalyzed asymmetric hydroboration of indoles,19
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1,2-dihydropyridines and 1,2-dihydroquinolines with excellent enantioselectivities. Recently
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Cu-catalyzed
enantioselective
hydroboration
of
N-CO2R-protected
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1,2-dihydroquinolines achieving high yields and excellent enantioselectivities.22 It was also found
that Cu-catalyzed asymmetric hydroboration could be successfully applied to the kinetic
resolution of racemic N-CO2R-2-substituted 1,2-dihydroquinolines with excellent resolution
efficiency under mild conditions (Scheme 1 a-b). 23
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Despite these great progresses, there were few reports on the asymmetric hydroboration of
allylic substrates.12 Naphthylallylic carbamates remain unexplored as the substrates in asymmetric
hydroboration so far. Promoted by the great utility of chiral amino organoboron compounds which
can be readily converted to the corresponding enantio-rich amino alcohols and other useful
molecules, we devote our efforts on the asymmetric hydroboration of the naphthylallylic
derivatives including naphthylallylic carbamates as a part of our continuous work. We herein
present an efficient approach to the synthesis of chiral noncyclic heteroatom organoboronates via
Cu-catalyzed enantioselective hydroboration of naphthylallylic derivatives, which provides chiral
organoboronates bearing heteroatom with high regio- and enantioselectivities of up to 96% ee
(Scheme 1).
Scheme 1. Cu-catalyzed asymmetric hydroboration of 1,2-dihydroquinolines and
naphthylallylic derivatives.
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RESULTS AND DISCUSSION
Inspired
by
our
previous
work,
we
prepared
(E)-tert-butyl
methyl-(3-(naphthalen-1-yl)-allyl)-carbamate 1a as the model substrate to optimize the
hydroboration conditions. Initially, the reaction was conducted in the presence of CuCl (5 mol%),
(R,Sp)-JosiPhos-1 (L1) (5 mol%), MeOK (20%) at 0 oC in THF (1.5 mL) and MeOH (2.0 equiv).
Although the desired product 2a was obtained in moderate yield, an excellent enantioselectivity
(98% ee) was achieved (Table 1, entry 1). It was found that this transformation could be catalyzed
by copper (II) precursors such as Cu(OAc)2 with similar enantioselectivity albeit the lower yield
observed (entry 2). The effect of bases on the reaction was then evaluated. When KOtBu was used
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as the base, the hydroboration product could be provided with excellent enantioselectivity (98%
ee), but a lower yield was obtained (entry 3). LiOtBu made the reaction ineffective and no product
was observed (entry 4). Encouraged by the excellent enantioselectivity achieved by
(R,Sp)-JosiPhos-1, some other JosiPhos derivatives were further screened in order to get
satisfactory yield. To our delight, in a shorter reaction time (S,Rp)-JosiPhos-2 (L2) could make the
substrate consume completely giving the hydroboration product 2a in much better yield (84%)
albeit a slightly decrease in enantioselectivity, 93% ee (entry 5). However, (R,Sp)-JosiPhos-3 (L3)
and (R,Sp)-JosiPhos-4 (L4) gave lower or extremely poor results (entries 6 and 7). Besides, several
commercial available chiral bisphosphine ligands (L5 – L9) were also evaluated in the
hydroboration. It was found that moderate enantioselectivity and yield (53% ee and 48% yield,
respectively) were afforded by (R,R)-QuinoxP* (L5) (entry 8), which exhibited high
enantioselectivity and activity in the asymmetric hydroboration of heterocyclic substrates. The
ligand (R)-DM-Segphos (L6), which was widely used and exhibited excellent performance in the
hydroboration of various noncyclic alkenes, only provided significantly decreased
enantioselectivity and yield (entry 9). Likewise, similar results were obtained when electron-rich
(S,R)-DuanPhos (L7), (R,R)-Me-DuPhos (L8) or (S,S)-f-spiroPhos (L9) were used in the reaction
(entry 10-12). The chiral monodentate ligand (R)-Monophos (L10) was also tested in this reaction,
but no product was obtained (entry 13). Despite the relatively lower yield, the highest
enantioselectivity achieved by (R,Sp)-JosiPhos-1 (L1) promoted us to improve the yield by further
optimization of the reaction time, temperature and solvent effect. However, it was revealed that
prolonging the reaction time or adjusting the temperature had no positive influence on the yield.
For example, even if the reaction proceeded for 15 hours, the yield still maintained as low as 58%
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(entry 14). Increasing the reaction temperature to 40 oC resulted lower yield and enantioselectivity
(entry 15). A variety of solvents including CH2Cl2, toluene, 1,4-dioxane, and 1,2-dimethoxyethane
(DME) were attempted using (R,Sp)-JosiPhos-1 (L1) as the ligand. In CH2Cl2 or 1,4-dioxane there
was almost no product observed (entries 16 and 17). Although the same excellent
enantioselectivity could be obtained in toluene or DME, the yields were not satisfactory (entries
18 and 19). Overall considering both yield and enantioselectivity, we consequently chose
CuCl/(S,Rp)-JosiPhos-2 (L2) (5 mol%) as the catalyst and MeOK as the base in THF for the
highest yield and relatively better enantioselectivity.
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Table 1. Reaction optimization.a
entry
1
ligand
L1
solvent
THF
THF
THF
THF
THF
THF
THF
THF
THF
base
yield (%)
58
ee (%)b
98
CH3OK
CH3OK
KOtBu
LiOtBu
CH3OK
CH3OK
CH3OK
CH3OK
CH3OK
2c
3
L1
30
94
L1
44
98
4
L1
trace
84
ND
93
5d
6
L2
L3
trace
21
ND
77
7
L4
8
L5
53
48
9
L6
32
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14e
15f
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L7
L8
L9
L10
L1
L1
L1
L1
L1
L1
THF
CH3OK
CH3OK
CH3OK
CH3OK
CH3OK
CH3OK
CH3OK
CH3OK
CH3OK
CH3OK
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57
THF
82
44
THF
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THF
trace
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ND
97
THF
THF
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85
DCM
1,4-dioxane
toluene
DME
trace
trace
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ND
ND
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a Reaction conditions: CuCl (0.025 mmol), ligand (0.025 mmol), 1a (0.5 mmol), B2pin2 (0.6 mmol), MeOK (0.1
o
b
c
mmol), solvent (1.5 mL), MeOH (1.0 mmol), 0 C – rt, 5 h. Determined by chiral HPLC analysis. Cu(OAc)2
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was used in this reaction. d The reaction with a reaction time of 2.5 h. e The reaction with a reaction time of 15 h. f
The reaction was carried out at 40 oC.
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With the optimal reaction condition in hand, we then prepared a series of naphthylallylic
compounds and applied them to the hydroboration for the investigation of the substrate scope
(Scheme 2). At the first, a variety of (E)-tert-butyl alkyl-(3-(naphthalen-1-yl)-allyl)-carbamates
were evaluated in the hydroboration under the optimal condition. This copper catalyst system
showed good activity and high enantioselectivity for substrates 1b – 1d furnishing boronates 2b –
2d in both good yields (76 – 82%) and excellent enantioselectivitives (93 – 94% ee). Changing the
alkyl substituent from methyl group to ethyl, propyl, butyl or benzyl on the nitrogen of N-Boc
substrates had no apparent effect on the enantioselectivities, whereas the yields decreased
gradually from 84% to 67%, which was possibly attributed to the bulkier and bulkier steric
hindrance of the alkyl substituents. It was notable that the substrate 1f bearing one more allylic
group could also provide the desired product 2f with high enantioselectivity as well as
regioselectivity. However, the dual-Boc-protected substrate 1g resulted in dramatically decrease in
the enantioselectivity and yield. The huge steric hindrance perhaps prevented the efficient
coordination of the catalyst to substrate. The substrate 1i bearing a smaller ethoxycarbonyl group
achieved both higher yield and enantioselectivity, 90% and 94% ee, respectively. Additionally,
2-naphtyl substrates 1h, 1j, 1k and 1l could be hydroborated providing the desired products 2h, 2j,
2k and 2l with good enantioselectivities from 88 – 90% ee. Remarkably, the NH substrate 1m
without alkyl substituent on the nitrogen could still achieve the comparable yield and
enantioselectivity. However, the bis-benzyl substituted 1r and the Z-isomer 1s only exhibited
extremely poor reactivity. It was worth noting that other types of naphthylallylic substrates such as
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(E)-diethyl (3-(naphthalen-1-yl)-allyl)-phosphonate 1n, (E)-3-(naphthalen-1-yl)-allyl acetate 1o,
and (E)-(3-(naphthalen-1-yl)-allyl)-(p-tolyl)-sulfane 1p were suitable for this hydroboration giving
the corresponding borylation products 2n and 2p with excellent enantioselectivities, 92 – 94% ee.
Especially, the substrate 1o provided the highest enantioselectivity of 96% ee and good yield, 82%.
Even if the substrate (E)-1-(but-1-en-1-yl)-naphthalene 1q without any heteroatom could also be
hydroborated to produce the 2q with similar enantioselectivity (92% ee) and yield (72%). The
absolute configuration of product 2f was determined and assigned to be (S) configuration by X-ray
crystallographic analysis of the corresponding single-crystal structure (See Figure S1 in
Supporting Information). Finally, the hydroboration of substrate 1a was carried out on a gram
scale (1.0 g) and the desired product 2a was obtained with maintained high conversion and
enantioselectivity.
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Scheme 2. Substrate Scope. a, b
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a
Unless otherwise mentioned, all reactions were carried out with CuCl (0.025 mmol), (R,Sp)-JosiPhos-2 (L2)
o
(0.025 mmol), 1 (0.5 mmol), B2pin2 (0.6 mmol), MeOK (0.1 mmol), THF (1.5 mL), MeOH (1.0 mmol), 0 C – rt,
2.5 h. b Enantiomeric excess values were determined by chiral HPLC or SFC analysis. c (R,Sp)-JosiPhos-1 (L1) was
used.
Chiral organoboronates are versatile synthetic intermediates that can be readily converted to
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numerous other useful derivatives (Scheme 3).1a-b Recently, the synthesis of chiral amino alcohols
has always attracted more and more attention from chemists because of their wide application as
key intermediates in chiral synthesis and biopharmaceuticals. The product 2c could be transformed
into the chiral β-amino alcohol 3 by oxidation with NaBO3 in high yield with maintained
enantioselectivity.19 The product 2e could also be successfully converted to the chiral γ-amino
alcohol 4 by homologation reaction without any loss of enantioselectivity.24 Chiral
organoboronates as significant coupling reagents played an important role in the construction of
C-C bond. The compound 5 could be prepared from the product 2i obtained by this strategy with
high enantioselectivity.25
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Scheme 3. Representative transformations of products 2.
On the basis of previous reports,7 a possible catalytic cycle for the hydroboration was proposed
as shown in Scheme 4. A diphosphine ligated Cu-OMe complex A was initially formed in the
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presence of CuCl, the ligand and MeOK, followed by the generation of borylcopper species B
with B2pin2. Subsequently, the coordination and addition of the species B to substrate 1 gave the
intermediate C. The resulting organocopper species reacted with MeOH to yield the protonated
product 2 and regenerate the copper methoxide A.
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Scheme 4. A proposed catalytic cycle for the hydroboration.
CONCLUSIONS
In conclusion, a Cu-catalyzed regio- and enantioselective hydroboration of naphthylallylic
carbamates has been first realized affording various chiral amino organoboron compounds with
good yields and high enantioselectivities of up to 94% ee. Moreover, other naphthylallylic
substrates including naphthylallylic phosphonates, acetates and sulfanes were also suitable for this
strategy affording the corresponding products in comparably yields and excellent
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enantioselectivities (up to 96% ee).
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EXPERIMENTAL SECTION
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General Information: All the air or moisture sensitive reactions and manipulations were
performed by using standard Schlenk techniques and in a nitrogen-filled glovebox. DME, THF
and toluene were distilled from sodium benzophenone ketyl. Dichloromethane was distilled from
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1
calcium hydride. Anhydrous MeOH was distilled from magnesium. H NMR and 13C NMR
(proton-decoupled) spectra were recorded on (400 MHz) spectrometers or (600 MHz)
spectrometers (CDC13 as the solvent used for the NMR analysis, with TMS as the internal
1
standard. Chemical shifts were reported upfield to TMS (0.00 ppm) for H NMR. Data is
represented as follows: chemical shift, integration, multiplicity (s = singlet, d = doublet, dd =
double of doublets, t = triplet, q = quartet, m = multiplet) and coupling constants (J) in Hertz (Hz).
Optical rotation was determined using Automatic polarimeter. HRMS were recorded on a mass
spectrometer with APCI or ESI.
Preparation and Analytical Data of Substrates 1: To a solution of NaH (60 wt. % in oil) (1.8 g,
45 mmol, 1.5 eq) in (THF, 80 mL) was added a solution of diethyl cyanomethylphosphonate (6.4 g,
36 mmol, 1.2 eq) in dry THF (30 mL) at 0 oC. After the mixture was stirred for 20 mins at 0 oC, a
solution of naphthaldehyde or substituted naphthaldehyde (30 mmol, 1.0 eq) in dry THF (40 mL)
was added dropwise at 0 oC. The reaction mixture was then allowed to warm to room temperature
and stirred overnight. After the conversion was complete, the solution was carefully quenched
with ice water and extracted with CH2Cl2. The organic layers were dried over anhydrous MgSO4,
filtered and evaporated. The residue was purified by silica gel column chromatography using
petroleum ether/EtOAc as an eluent (PE/EA = 10/1, Rf = 0.3) to give the corresponding
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(E)-3-(naphthalen-1-yl)-acrylonitrile or substituted compounds as white solid in 92 – 96%
yields.26a
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solution of AlCl3 (1.3 g, 10 mmol, 0.5 eq) in dry Et2O (30 ml) at 0 C. After the mixture was
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stirred for 30 mins at 0 C, a solution of (E)-3-(naphthalen-1-yl)-acrylonitrile (3.58 g, 20 mmol,
1.0 eq) in Et2O (30 ml) was added and stirred for 30 mins. The reaction was carefully quenched
with H2O and filtered. The filtrate was extracted by EtOAc. The organic layers were dried over
anhydrous MgSO4, filtered and evaporated. The residue was purified by silica gel column
chromatography using CH2Cl2/MeOH as an eluent (CH2Cl2/MeOH = 10/1, Rf = 0.25) to give the
corresponding (E)-3-(naphthalen-1-yl)-prop-2-en-1-amine or substituted compounds as colorless
oil with 70 –75% yields.26b
To a solution of (E)-3-(naphthalen-1-yl)-prop-2-en-1-amine (0.79 g, 4.3 mmol, 1.0 eq) in
MeCN (20 mL) was added DMAP (4.9 mg, 0.04 mmol, 0.95%). After the mixture was stirred for
20 mins at room temperature, a solution of di-tert-butyl decarbonate (2.8 g, 12.9 mmol, 1.5 eq) or
diethyl pyrocarbonate (2.1 g, 12.9 mmol, 1.5 eq) was added. The reaction was quenched with
aqueous NH4Cl solution and extracted with EtOAc after completion monitored by TLC. The
organic layers were dried over anhydrous MgSO4, filtered and evaporated. The residue was
purified by silica gel column chromatography using petroleum ether/EtOAc as an eluent (PE/EA,
10/1
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20/1,
Rf
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0.3)
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corresponding
(E)-tert-butyl
(3-(naphthalen-1-yl)-allyl)-carbamate or (E)-ethyl (3-(naphthalen-1-yl)-allyl)-carbamate as a white
solid with yields of 82 – 84%.26c
The previously obtained product (E)-tert-butyl (3-(naphthalen-1-yl)-allyl)-carbamate (1.4 g, 5
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mmol, 1.0 eq) and KOH (1.4 g, 25 mmol, 5.0 eq) were dissolved in DMSO (15 mL) under a
nitrogen atmosphere. After the mixture was stirred for 20 mins, the halohydrocarbon (7.5 mmol,
1.5 eq) or Boc2O (3.3 g, 15 mmol, 3 eq) was then added and stirred at room temperature (60 oC for
1g) overnight. After quenched with aqueous NH4Cl, the resulting mixture was extracted three
times with CH2Cl2, dried over anhydrous MgSO4 and filtered. The residue was purified by silica
gel column chromatography (petroleum ether/EtOAc, 10/1 – 30/1, Rf = 0.3) to give the substrates
1a – 1l and 1s as colorless oil in 46 – 56% yields.26d
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(E)-tert-butyl methyl-(3-(naphthalen-1-yl)-allyl)-carbamate (1a): 0.83 g, yield: 56%; 1H NMR
(CDCl3, 600 MHz) δ: 8.13 – 8.12 (1 H, m), 7.85 – 7.84 (1 H, m), 7.78 – 7.77 (1 H, m), 7.59 – 7.44
(4 H, m), 7.23 (1 H, d, J = 15.1 Hz), 6.19 (1 H, s), 4.10 (2 H, d, J = 40.7 Hz), 2.98 (3 H, s), 1.55 (9
H, s). 13C{1H}NMR (CDCl3, 150 MHz) δ: 155.7, 134.5, 133.7, 131.2, 128.6, 128.5, 128.0, 126.1,
125.8, 125.7, 124.0, 123.8, 79.4, 51.2, 33.8, 28.6. TOF-HRMS Calcd. for C19H23NO2Na [M+Na+]:
320.1621, found 320.1618.
1
(E)-tert-butyl ethyl-(3-(naphthalen-1-yl)-allyl)-carbamate (1b): 0.86 g, yield: 55%; H NMR
(CDCl3, 400 MHz) δ: 8.10 (1 H, d, J = 7.9 Hz), 7.85 (1 H, d, J = 7.0 Hz), 7.78 (1 H, d, J = 8.2 Hz),
7.58 (1 H, d, J = 6.9 Hz), 7.50 – 7.44 (3 H, m), 7.25 – 7.20 (1 H, m), 6.21 – 6.18 (1 H, m), 4.10 (2
H, s), 3.37 (2 H, s), 1.51 (9 H, s), 1.18 (3 H, t, J = 7.2 Hz). 13C{1H}NMR (CDCl3, 150 MHz) δ:
155.5, 134.8, 133.8, 131.3, 129.5, 128.7, 128.0, 126.2, 125.9 125.8, 124.0, 123.9, 79.5, 49.1, 41.7,
29.9, 28.5, 13.9. TOF-HRMS Calcd. for C20H25NO2Na [M+Na+]: 334.1777, found 334.1776.
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(E)-tert-butyl (3-(naphthalen-1-yl)-allyl)-(propyl)-carbamate (1c): 0.88 g, yield: 54%; H
NMR (CDCl3, 600 MHz) δ: 8.09 (1 H, d, J = 8.1 Hz), 7.85 (1 H, d, J = 7.6 Hz), 7.77 (1 H, d, J =
8.2 Hz), 7.57 (1 H, d, J = 6.8 Hz), 7.54 – 7.46 (2 H, m), 7.44 (1 H, t, J = 7.6 Hz), 7.20 (1 H, d, J =
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14.5 Hz), 6.19 (1 H, s), 4.12 – 4.06 (2 H, m), 3.27 (2 H, d, J = 23.9 Hz), 1.62 (2 H, s), 1.50 (9 H,
s), 0.92 (3 H, t, J = 7.3 Hz). 13C{1H}NMR (CDCl3, 150 MHz) δ: 155.8, 134.8, 133.7, 131.2, 129.5,
128.6, 127.9, 126.1, 125.9, 125.7, 124.0, 123.8, 79.5, 48.6, 28.6, 21.9, 11.4. TOF-HRMS Calcd.
for C21H27NO2Na [M+Na+]: 348.1934, found 348.1937.
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(E)-tert-butyl butyl-(3-(naphthalen-1-yl)-allyl)-carbamate (1d): 0.88 g, yield: 52%; H NMR
(CDCl3, 400 MHz) δ: 8.12 (1 H, d, J = 7.9 Hz), 7.91 – 7.83 (1 H, m), 7.79 (1 H, d, J = 8.1 Hz),
7.60 (1 H, d, J = 7.1 Hz), 7.57 – 7.42 (3 H, m), 7.23 (1 H, d, J = 17.4 Hz), 6.22 (1 H, s), 4.11 (2 H,
d, J = 22.5 Hz), 3.32 (2 H, s), 1.66 – 1.57 (2 H, m), 1.53 (9 H, s), 1.38 (2 H, dt, J = 14.6, 7.3 Hz),
0.98 (3 H, t, J = 7.3 Hz). 13C{1H}NMR (CDCl3, 100 MHz) δ: 156.2, 135.3, 134.2, 131.7, 129.9,
129.1, 128.4, 126.6, 126.3, 126.2, 124.5, 124.3, 79.9, 49.6, 47.0, 31.2, 29.1, 27.5, 20.7, 14.5.
TOF-HRMS Calcd. for C22H29NO2Na [M+Na+]: 362.209, found 362.2087.
1
(E)-tert-butyl benzyl-(3-(naphthalen-1-yl)-allyl)-carbamate (1e): 0.88 g, yield: 47%; H NMR
(CDCl3, 400 MHz) δ: 8.04 (1 H, d, J = 7.7 Hz), 7.91 – 7.83 (1 H, m), 7.79 (1 H, d, J = 8.2 Hz),
7.52 (3 H, t, J = 9.2 Hz), 7.44 (1 H, d, J = 7.5 Hz), 7.41 – 7.29 (5 H, m), 7.17 (1 H, d, J = 15.6 Hz),
6.17 (1 H, s), 4.58 (2 H, s), 4.10 (2 H, d, J = 42.3 Hz), 1.54 (9 H, s). 13C{1H}NMR (CDCl3, 100
MHz) δ: 138.5, 134.7, 133.7, 131.2, 128.7, 128.0, 127.4, 126.1, 125.9, 125.7, 123.9, 80.1, 49.8,
48.7, 28.6, 27.0. TOF-HRMS Calcd. for C25H27NO2Na [M+Na+]: 396.1934, found 396.1939.
1
(E)-tert-butyl allyl-(3-(naphthalen-1-yl)-allyl)-carbamate (1f): 0.74 g, yield: 46%; H NMR
(CDCl3, 400 MHz) δ: 8.13 (1 H, d, J = 8.3 Hz), 7.90 – 7.82 (1 H, m), 7.78 (1 H, d, J = 8.2 Hz),
7.60 (1 H, d, J = 7.1 Hz), 7.50 (3 H, ddt, J = 17.7, 15.4, 4.4 Hz), 7.24 (1 H, d, J = 15.5 Hz), 6.38 –
6.07 (1 H, m), 5.89 (1 H, d, J = 5.2 Hz), 5.40 – 5.04 (2 H, m), 4.03 (4 H, d, J = 59.4 Hz), 1.56 (9 H,
s). 13C{1H}NMR (CDCl3, 100 MHz) δ: 155.6, 134.8, 134.3, 133.8, 131.3, 129.0, 128.7, 128.1,
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126.2, 125.9, 125.8, 124.1, 123.9, 116.5, 79.9, 49.1, 28.6, 27.1. TOF-HRMS Calcd. for
C21H25NO2Na [M+Na+]: 346.1777, found 346,1783.
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(E)-ditert-butyl (3-(naphthalen-1-yl)-allyl)-carbamate (1g): 1.0 g, yield: 53%; 1H NMR
(CDCl3, 400 MHz) δ: 8.05 – 7.97 (1 H, m), 7.78 – 7.73 (1 H, m), 7.68 (1 H, d, J = 8.1 Hz), 7.41 (1
H, d, J = 7.1 Hz), 7.41 – 7.34 (3 H, m), 7.20 (1 H, d, J = 15.6 Hz), 6.15 (1 H, dt, J = 15.5, 6.1 Hz),
4.36 (2 H, d, J = 6.1 Hz), 1.45 (18 H, s). 13C{1H}NMR (CDCl3, 100 MHz) δ: 152.2, 134.4, 133.3,
130.9, 129.3, 128.2, 128.1, 127.7, 125.7, 125.5, 125.4, 123.7, 82.2, 48.1, 27.9. TOF-HRMS Calcd.
for C23H29NO4Na [M+Na+]: 406.1988, found 406.1983.
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(E)-tert-butyl methyl-(3-(naphthalen-2-yl)-allyl)-carbamate (1h): 0.73 g, yield: 49%; 1H NMR
(CDCl3, 600 MHz) δ: 7.78 (3 H, t, J = 8.5 Hz), 7.71 (1 H, s), 7.58 (1 H, dd, J = 8.5, 1.7 Hz), 7.48
– 7.39 (2 H, m), 6.62 (1 H, d, J = 15.6 Hz), 6.28 (1 H, s), 4.03 (2 H, s), 2.90 (3 H, s), 1.50 (9 H, s).
13C{1H}NMR (CDCl3, 100 MHz) δ: 155.9, 134.3, 133.7, 133.1, 128.3, 128.0, 127.8, 126.4, 126.3,
125.9, 123.6, 79.7, 51.3, 33.9, 29.8, 28.6. TOF-HRMS Calcd. for C19H23NO2Na [M+Na+]:
320.1621, found 320.1618.
1
(E)-ethyl methyl-(3-(naphthalen-1-yl)-allyl)-carbamate (1i): 0.65 g, yield: 48%; H NMR
(CDCl3, 400 MHz) δ: 8.10 (1 H, d, J = 7.8 Hz), 7.90 – 7.81 (1 H, m), 7.78 (1 H, d, J = 8.2 Hz),
7.58 (1 H, d, J = 7.1 Hz), 7.56 – 7.40 (3 H, m), 7.24 (1 H, d, J = 15.3 Hz), 6.19 (1 H, s), 4.19 (4 H,
dq, J = 22.8, 7.1 Hz), 2.99 (3 H, s), 1.31 (3 H, t, J =7.1 Hz). 13C{1H}NMR (CDCl3, 100 MHz) δ:
156.7, 134.5, 133.7, 131.2, 129.9, 128.7, 128.3, 128.1, 126.2, 125.9, 125.7, 124.1, 123.8, 100.0,
61.5, 51.1, 33.6, 14.9. TOF-HRMS Calcd. for C17H19NO2Na [M+Na+]: 292.1308, found 292.1305.
1
(E)-ethyl methyl-(3-(naphthalen-2-yl)-allyl)-carbamate (1j): 0.58 g, yield: 43%; H NMR
(CDCl3, 400 MHz) δ: 7.83 – 7.76 (3 H, m), 7.72 (1 H, d, J = 1.6 Hz), 7.59 (1 H, dd, J = 8.6, 1.7
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Hz), 7.48 – 7.41 (2 H, m), 6.64 (1 H, t, J = 12.1 Hz), 6.29 (1 H, s), 4.20 (2 H, q, J = 7.1 Hz), 4.10
(2 H, dd, J = 16.7, 10.1 Hz), 2.94 (3 H, d, J = 12.7 Hz), 1.30 (3 H, t, J = 7.1 Hz). 13C{1H}NMR
(CDCl3, 100 MHz) δ: 157.1, 134.7, 134.1, 133.6, 133.1, 132.5, 128.8, 128.5, 128.2, 126.9, 126.5,
125.9, 124.1, 70.0, 51.3, 34.0, 15.4. TOF-HRMS Calcd. for C17H19NO2Na [M+Na+]: 292.1308,
found 292.1305.
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(E)-ethyl (3-(6-methoxynaphthalen-2-yl)-allyl)-(methyl)-carbamate (1k): 0.69 g, yield: 46%;
1H NMR (CDCl3, 400 MHz) δ: 7.66 (3 H, m), 7.54 (1 H, d, J = 8.5 Hz), 7.11 (2 H, d, J = 13.7 Hz),
6.60 (1 H, d, J = 15.8 Hz), 6.21 (1 H, d, J = 15.3 Hz), 4.17 (2 H, q, J = 7.2 Hz), 4.06 (2 H, s), 3.90
(3 H, s), 2.92 (3 H, s), 1.28 (3 H, t, J = 6.9 Hz). 13C{1H}NMR (CDCl3, 100 MHz) δ: 157.9, 134.3,
132.1, 129.6, 129.0, 127.2, 126.2, 124.2 , 119.1, 105.9, 100.0, 61.5, 55.4, 51.1, 14.9. TOF-HRMS
Calcd. for C18H21NO3Na [M+Na+]: 322.1413, found 322.1419.
(E)-tert-butyl (3-(7-bromonaphthalen-2-yl)allyl)(methyl)carbamate (1l): 0.4 g, yield: 46%; 1H
NMR (CDCl3, 400 MHz) δ: 7.94 (1 H, d, J = 1.6 Hz), 7.73 (1 H, d, J = 8.4 Hz), 7.65 (1 H, d, J =
8.7 Hz), 7.62 – 7.55 (2 H, m), 7.49 (1 H, dd, J = 8.7, 2.0 Hz), 6.59 (1 H, d, J = 15.7 Hz), 6.27 (1 H,
dt, J = 13.7, 5.8 Hz), 4.02 (2 H, s), 2.89 (3 H, s), 1.48 (9 H, s). 13C{1H}NMR (CDCl3, 100 MHz) δ:
155.8, 135.4, 134.8, 131.4, 130.0, 129.4, 129.3, 128.2, 126.8, 125.2, 124.1, 120.4, 79.7, 34.0, 28.6.
TOF-HRMS Calcd. for C19H23NO2Br [M+H+]: 376.0906, found 376.0912.
1
(E)-tert-butyl (3-(naphthalen-1-yl)allyl)carbamate (1m): 0.6 g, yield: 84%; H NMR (CDCl3,
600 MHz) δ: 7.93 (1 H, ddt, J = 5.3, 3.0, 1.6 Hz), 7.85 (1 H, ddt, J = 8.2, 5.6, 2.4 Hz), 7.78 (1 H,
d, J = 8.2 Hz), 7.51 – 7.47 (2 H, m), 7.43 (1 H, dd, J = 8.1, 7.1 Hz), 7.27 (1 H, d, J = 7.4 Hz), 7.03
(1 H, d, J = 11.3 Hz), 5.97 (1 H, dt, J = 11.5, 6.7 Hz), 4.50 (1 H, s), 3.87 (2 H, s), 1.41 (9 H, s).
13C{1H}NMR (CDCl3, 150 MHz) δ: 155.8, 133.6, 133.5, 131.8, 130.5, 129.6, 128.5, 127.9, 126.6,
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126.2, 125.9, 125.3, 124.8, 79.5, 39.1, 28.5. TOF-HRMS Calcd. for C18H21NO2Na [M+Na+]:
306.1464, found 306.1464.
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Procedure for the synthesis of (E)-diethyl-(3-(naphthalen-1-yl)-allyl)-phosphonate 1n: To a
stirred solution of NaH (60 wt. % in oil) (0.44 g, 11 mmol, 1.1 eq) in dry THF (20 mL) was added
triethyl phosphonoacetate (2.24 g, 10 mmol, 1.0 eq) in dry THF (20 mL) at 0 oC. After 20 mins, a
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solution of 1-naphthaldehyde (1.56 g, 10 mmol, 1.0 eq) was added at 0 C. The reaction was
quenched after stirred for 10 h with the aqueous NH4Cl and extracted with CH2Cl2. The organic
layers were dried over anhydrous MgSO4, filtered and evaporated. The residue was purified by
column chromatography on silica gel (PE/EA = 10/1, Rf = 0.5) to give the desired product
(E)-ethyl 3-(naphthalen-1-yl)-acrylate as a colorless oil in 86% yield.
A solution of (E)-ethyl 3-(naphthalen-1-yl)-acrylate (1.58 g, 6.98 mmol, 1.0 eq) in toulene (16.8
mL) was cooled to 0 oC and treated with diisobutylaluminium hydride (16.75 mmol, 2.4 eq). After
stirred at 0 oC for 30 mins, the reaction was quenched with water. The organic layer was separated
and the aqueous layer was extracted with EtOAc. The combined organic layers were dried over
MgSO4, filtered and concentrated under vacuum. The crude material was purified by flash column
chromatography on silica gel (PE/EA
=
1/1, Rf
=
0.35) to give the product
(E)-3-(naphthalene-1-yl)- prop-2-en-1-ol as a colorless crystals with the yield of 90%.
A solution of tribromophosphine (3.17 g, 11.7 mmol, 1.85 eq) was slowly added to an ice-cold
solution of (E)-3-(naphthalen-1-yl)-prop-2-en-1-ol (6.3 mmol, 1.0 eq) in Et2O (25 mL). The
mixture was stirred for 30 mins at 0 °C and 2 h at room temperature. After the conversion was
complete, the reaction was quenched with water and extracted with CH2Cl2. The organic layers
were dried over MgSO4, filtered and evaporated. The residue was purified by column
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chromatography on silica gel (PE/EA = 15/1, Rf = 0.5) to give the desired product
(E)-1-(3-bromoprop-1-en-1-yl)-naphthalene as a colorless oil with a quantitative yield.26a
To an ice-cold solution of diethyl phosphite (3.3 mmol 1.1 eq) in THF (15 mL) was added
n-BuLi (3.3 mmol, 2.5 M in hexanes, 1.1 eq). After the mixture was stirred for 15 mins at -10 °C,
a solution of (E)-1-(3-bromoprop-1-en-1-yl)-naphthalene (3.0 mmol, 1.0 eq) in THF (5 mL) was
added dropwise. After 3 h at -10 °C, a saturated aqueous solution of NH4Cl was added and the
mixture was allowed to warm to room temperature. The reaction mixture was diluted with EtOAc
and washed with water. The organic layer was separated and the aqueous layer was extracted with
EtOAc. The combined organic layers were dried over MgSO4, filtered and concentrated under
vacuum. Purification by column chromatography on silica gel (PE/EA = 1/1, Rf = 0.25) to give the
desired product (E)-diethyl-(3-(naphthalen-1-yl)-allyl)-phosphonate 1n as a colorless oil in 53%
yield.27
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(E)-diethyl (3-(naphthalen-1-yl)-allyl)-phosphonate (1n): 0.48 g, yield: 53%; 1H NMR (CDCl3,
600 MHz) δ: 8.09 (1 H, d, J = 8.0 Hz), 7.83 (1 H, d, J = 7.6 Hz), 7.76 (1 H, d, J = 8.2 Hz), 7.56 (1
H, d, J = 7.1 Hz), 7.52 – 7.45 (2 H, m), 7.45 – 7.40 (1 H, m), 7.27 (1 H, dd, J = 15.5, 5.2 Hz), 6.19
(1 H, m), 4.15 (4 H, m), 2.89 (2 H, dd, J = 22.2, 7.5 Hz), 1.33 (6 H, t, J = 7.1 Hz). 13C{1H}NMR
(CDCl3, 100 MHz) δ: 134.3, 133.3, 131.8, 131.7, 130.7, 128.2, 127.7, 125.8, 125.5, 125.3, 123.6,
123.4, 121.8, 121.7, 61.7, 31.8, 30.4, 16.2. TOF-HRMS Calcd. for C17H22O3P [M+H+]: 305.1301,
found 305.1307.
Procedure for the synthesis of (E)-3-(naphthalen-1-yl)-allyl acetate 1o: To a solution of
palladium diacetate (56 mg, 0.25 mmol, 5 mol %) and silver carbonate (0.83 g, 3.0 mmol, 0.6 eq)
in toluene (15 mL) was added 1-iodonaphthalene (1.27 g, 5.0 mmol, 1.0 eq) and allyl acetate (1.0
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g, 10 mmol, 2.0 eq). The resulting mixture was heated at reflux for 12 h. After the conversion was
complete, the reaction mixture was then concentrated by evaporation. The residue was purified by
silica gel column chromatography using petroleum ether/EtOAc as an eluent (PE/EA = 20/1, Rf =
0.3) to give the corresponding (E)-3-(naphthalen-1-yl)-allyl acetate 1o as a colorless oil in 66%
yield.28
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(E)-3-(naphthalen-1-yl)-allyl acetate (1o): 0.75 g, yield: 66%; H NMR (CDCl3, 400 MHz) δ:
8.12 (1 H, d, J = 8.1 Hz), 7.87 (1 H, d, J = 8.8 Hz), 7.81 (1 H, d, J = 8.2 Hz), 7.62 (1 H, d, J = 7.1
Hz), 7.59 – 7.38 (4 H, m), 6.33 (1 H, dt, J = 15.6, 6.3 Hz), 4.92 – 4.81 (2 H, m), 2.16 (3 H, s).
13C{1H}NMR (CDCl3, 100 MHz) δ: 170.6, 133.7, 133.4, 131.1, 130.9, 128.4, 128.2, 126.2, 126.0,
125.7, 125.4, 123.9, 123.5, 64.9, 20.8. TOF-HRMS Calcd. for C15H14O2Na [M+Na+]: 249.0886,
found 249.0884.
Procedure for the synthesis of (E)-(3-(naphthalen-1-yl) allyl)-(p-tolyl)-sulfane 1p: To an
ice-cold solution of (E)-1-(3-bromoprop-1-en-1-yl)-naphthalene (1.46 g, 5.9 mmol, 1 eq) in Et2O
(15 mL) was added triethylamine (7.38 mmol, 1.25 eq) and 4-methylbenzenethiol (0.82 g, 7.4
mmol, 1.25 eq) at 0 °C. After the resulting mixture was stirred for 20 mins at 0 °C, the reaction
mixture was then allowed to stir at room temperature for 3 d. After the conversion was complete,
the organic phase was subsequently washed with water (30 mL), 2 M aqueous HCl-solution (30
mL), and brine (30 mL), and dried over Na2SO4, filtered and evaporated. The crude product was
recrystallized from the solvent mixture of EA and PE (1:10) to give the corresponding product
(E)-(3-(naphthalen-1-yl) allyl)-(p-tolyl)-sulfane 1p as a white solid in 68% yield.27
(E)-(3-(naphthalen-1-yl)-allyl)-(p-tolyl)-sulfane (1p): light yellow solid, MP: 90– 922 °C, 1.17 g,
yield: 68%; 1H NMR (CDCl3, 600 MHz) δ: 7.87 – 7.74 (3 H, m), 7.55 – 7.37 (6 H, m), 7.15 (2 H,
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d, J = 7.9 Hz), 7.04 (1 H, d, J = 15.4 Hz), 6.32 – 6.19 (1 H, m), 3.77 (2 H, dd, J = 7.3, 1.2 Hz),
2.36 (3 H, s). 13C{1H}NMR (CDCl3, 100 MHz) δ: 137.0, 134.9, 133.6, 132.1, 131.7, 131.2, 130.1,
129.9, 128.6, 128.5, 128.0, 126.0, 125.9, 125.7, 124.1, 38.5, 21.3. TOF-HRMS Calcd. for
C20H18SNa [M+Na+]: 313.1021, found 313.1028.
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Procedure for the synthesis of (E)-1-(but-1-en-1-yl)-naphthalene (1q): A solution of
ammonium acetate (0.39 g, 5.0 mmol, 0.25 eq) in nitromethane (25 mL) was heated to 90 °C and a
solution of 1-naphthaldehyde (3.12 g, 20 mmol, 1.0 eq) was added dropwise. The resulting
mixture was heated at reflux for 6 h. Aqueous of water was added and the mixture was extracted
three times with CH2Cl2, dried over MgSO4, and filtered. The crude material was purified by silica
gel column chromatography using petroleum ether/EtOAc as an eluent (PE/EA = 25/1, Rf = 0.3)
to give the (E)-1-(2-nitrovinyl)-naphthalene as a yellow oil in the yield of 60%.29
To a solution of (E)-1-(2-nitrovinyl)-naphthalene (0.6 g, 3.0 mmol, 1.0 eq) in Et2O (30 mL) was
added triethylborane (12 mmol, in THF, 4.0 eq) at room temperature. After 30 mins, the starting
material was consumed. Aqueous of water was added and the mixture was extracted three times
with EtOAc. The organic phase was dried over MgSO4 and filtered. Purification by column
chromatography on silica gel using petroleum ether as an eluent (Rf = 0.5) to give the desired
product (E)-1-(but-1-en-1-yl)-naphthalene 1q as a colorless oil in 78% yield.
(E)-1-(but-1-en-1-yl)-naphthalene (1q): 0.43 g, yield: 78%; 1H NMR (CDCl3, 600 MHz) δ: 8.17
(1 H, d, J = 8.2 Hz), 7.87 (1 H, d, J = 8.2 Hz), 7.77 (1 H, d, J = 8.2 Hz), 7.59 (1 H, d, J = 7.1 Hz),
7.56 – 7.48 (2 H, m), 7.46 (1 H, t, J = 7.7 Hz), 7.15 (1 H, d, J = 15.6 Hz), 6.32 (1 H, m), 2.42 –
2.36 (2 H, m), 1.22 (3 H, t, J = 7.5 Hz). 13C{1H}NMR (CDCl3, 100 MHz) δ: 136.1, 135.9, 133.8,
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131.3, 128.6, 127.3, 126.1, 125.9, 125.8, 125.7, 124.1, 123.6, 26.6, 13.9. TOF-HRMS Calcd. for
C14H15 [M+H+]: 183.1168, found 183.1165.
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(E)-N,N-dibenzyl-3-(naphthalen-1-yl)prop-2-en-1-amine (1r): 0.58 g, yield: 90%; H NMR
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(CDCl3, 600 MHz) δ: 8.10 (1 H, d, J = 7.7 Hz), 7.88 – 7.82 (1 H, m), 7.78 (1 H, d, J = 8.2 Hz),
7.57 (1 H, d, J = 7.0 Hz), 7.53 – 7.43 (7 H, m), 7.38 – 7.26 (7 H, m), 6.35 (1 H, ddt, J = 15.3, 6.4,
2.3 Hz), 3.73 (4 H, s), 3.41 – 3.33 (2 H, m). 13C{1H}NMR (CDCl3, 150 MHz) δ: 139.8, 135.2,
133.7, 131.2, 131.1, 129.8, 128.9, 128.6, 128.4, 127.8, 127.0, 126.1, 125.8, 125.7, 123.9, 58.2,
56.1. The analytical data are consistent with the literature.30
1
(Z)-tert-butyl methyl(3-(naphthalen-1-yl)allyl)carbamate (1s): 0.35 g, yield: 30%; H NMR
(acetone-D6, 400 MHz) δ: 8.11 (1 H, d, J = 8.2 Hz), 7.92 – 7.84 (1 H, m), 7.75 (1 H, dd, J = 6.9,
2.6 Hz), 7.54 – 7.44 (2 H, m), 7.43 – 7.37 (2 H, m), 7.06 (1 H, dd, J = 43.0, 13.6 Hz), 5.11 (1 H, dt,
J = 14.0, 6.8 Hz), 3.83 (2 H, d, J = 6.6 Hz), 2.95 (3 H, s), 1.41 (9 H, s). 13C{1H}NMR (CDCl3, 100
MHz) δ: 153.0, 137.5, 134.0, 132.0, 130.1, 129.7, 128.8, 127.0, 126.0, 125.7, 125.6, 134.0, 107.0,
106.3, 81.0, 33.7, 31.3, 28.4. TOF-HRMS Calcd. for C19H23NO2Na [M+Na+]: 320.1621, found
320.1618.
General procedure of Cu-catalyzed enantioselective hydroboration: In a nitrogen-filled
glovebox, CuCl (0.025 mmol, 5 mol%), (S, Rp)-JosiPhos-2 (L2) (0.025 mmol, 5 mol%), B2pin2
(0.6 mmol, 1.2 eq), MeOK (0.1 mmol, 0.2 eq) and dry THF (1.0 mL) were placed in an oven-dried
Schleck tube which was sealed with a rubber plug. The reaction mixture stirred 10 mins at room
temperature. The Schleck tube was then removed from glovebox. After substrates 1 (0.50 mmol,
1.0 eq) was added to the mixture at 0 °C, MeOH (1.0 mmol, 2.0 eq) was added dropwise. After
stirred for 30 mins at 0 °C, the reaction mixture was then allowed to warm to ambient temperature
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and stirred for 2 h. The reaction mixture was passed through a short silica gel column eluting with
Et2O. The crude mixture was purified by chromatography on silica gel using petroleum
ether/EtOAc as an eluent (PE/EA/ = 2/1 to 20/1) to give the n products 2 as light yellow solids or
oil. The ee values of 2 were determined by HPLC or SFC analysis on a chiral stationary phase.
The procedure of hydroboration of 1a on a gram scale: In a nitrogen-filled glovebox, CuCl
(16.6 mg, 0.17 mmol), (S, Rp)-JosiPhos-2 (L2) (99.9 mg, 0.17 mmol), B2pin2 (1.02 g, 4.0 mmol),
MeOK (47.1 mg, 0.67 mmol) and dry THF (10.0 mL) were placed in an oven-dried Schleck tube.
The reaction mixture stirred 10 mins at room temperature. The Schleck tube was then removed
from glovebox. After substrate 1a (1.0 g, 3.36 mmol) was added to the mixture at 0 °C, MeOH
(6.72 mmol) was added dropwise. After stirred for 30 mins at 0 °C, the reaction mixture was then
allowed to warm to ambient temperature and stirred for 2h. The reaction mixture was passed
through a short silica gel column eluting with Et2O. The crude mixture was purified by
chromatography on silica gel using petroleum ether/EtOAc as an eluent (PE/EA/ = 10/1) to give
the product 2a as a light yellow oil with the similar yield and enantioselectivity (1.22 g, 85% yield;
94% ee).
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tert-butyl
methyl-(3-(naphthalen-1-yl)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-propyl)-carbam
ate (2a): light yellow oil, 178.7 mg, yield: 84%; 1H NMR (CDCl3, 400 MHz) δ: 8.04 (1 H, d, J =
8.2 Hz), 7.81 (1 H, d, J = 8.5 Hz), 7.68 (1 H, d, J = 8.3 Hz), 7.41 (4 H, dq, J = 37.9, 8.4, 7.4 Hz),
3.63 – 2.95 (4 H, m), 2.87 (3 H, d, J = 44.5 Hz), 1.95 (1 H, d, J = 11.9 Hz), 1.43 (9 H, d, J = 32.9
Hz), 1.12 (12 H, d, J = 18.7 Hz). 13C{1H}NMR (CDCl3, 100 MHz) δ: 156.1, 134.0, 132.1, 128.8,
126.5, 125.8, 125.3, 124.0, 121.2, 83.4, 79.4, 51.0, 32.0, 28.5, 24.9. TOF-HRMS Calcd. for
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C25H36BNO4Na [M+Na+]: 448.2634, found 448.2636. 93% ee; [α]D = -19.85 (c = 1.0, CHCl3);
HPLC condition: Lux 5μm Amylose-1 (250 × 4.60 mm) (250 × 4.60 mm), ipa : hex = 5 : 95, 1.0
mL/min, 254 nm; tA = 3.9 min (minor), tB = 4.3 min (major).
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tert-butyl
ethyl-(3-(naphthalen-1-yl)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-propyl)-carbamat
e (2b): light yellow solid, MP: 95 – 97 °C, 180.2 mg, yield: 82%; 1H NMR (CDCl3, 400 MHz) δ:
8.04 (1 H, d, J = 8.0 Hz), 7.85 – 7.76 (1 H, m), 7.67 (1 H, d, J = 8.1 Hz), 7.53 – 7.40 (2 H, m),
7.36 (2 H, p, J = 6.8 Hz) 3.55 – 3.37 (2 H, m), 3.33 – 3.01 (4 H, m), 1.96 (1 H, s), 1.43 ( 9 H, s),
1.11 (15 H, d, J = 19.1 Hz). 13C{1H}NMR (CDCl3, 100 MHz) δ: 155.8, 133.9, 132.1, 128.7, 126.7,
126.4, 125.7, 125.4, 125.3, 124.0, 83.3, 79,2, 48.1, 42.0, 32.0, 29.8, 28.6, 24.9, 14.2. TOF-HRMS
Calcd. for C26H39BNO4 [M+H+]: 440.2971, found 440.2968. 93% ee; [α]D = -17.09 (c = 1.0,
17
CHCl3); HPLC condition: Lux 5μm Amylose-1 (250 × 4.60 mm) (250 × 4.60 mm), ipa : hex = 2 :
98, 1.0 mL/min, 254 nm; tA = 4.2 min (minor), tB = 4.6 min (major).
tert-butyl
(3-(naphthalen-1-yl)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-propyl)-(propyl)-carba
mate (2c): light yellow solid, MP: 97 – 99 °C, 179.1 mg, yield: 79%; 1H NMR (CDCl3, 600 MHz)
δ: 8.05 (1 H, s), 7.81 (1 H, d, J = 7.9 Hz), 7.67 (1 H, d, J = 8.0 Hz), 7.46 (2 H, dt, J = 25.6, 7.0 Hz),
7.42 – 7.32 (2 H, m), 3.43 (2 H, d, J = 40.5 Hz), 3.13 (4 H, d, J = 26.3 Hz), 2.12 – 1.87 (1 H, m),
1.58 – 1.34 (11 H, m), 1.11 (12 H, d, J = 29.9 Hz), 0.89 – 0.79 (3 H, m). 13C{1H}NMR (CDCl3,
100 MHz) δ: 155.9, 134.0, 132.1, 128.7, 126.7, 126.4, 125.7, 125.3, 124.1, 83.3, 79.1, 48.8, 32.0,
29.8, 28.5, 24.9, 21.6, 11.4. TOF-HRMS Calcd. for C27H40BNO4Na [M+Na+]: 476.2948, found
476.2942. 94% ee; [α]D20 = -12.50 (c = 1.0, CHCl3); HPLC condition: Lux 5μm Amylose-1 (250 ×
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4.60 mm) (250 × 4.60 mm), ipa : hex = 2 : 98, 1.0 mL/min, 254 nm; tA = 3.7 min (minor), tB = 4.1
min (major).
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butyl-(3-(naphthalen-1-yl)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-propyl)-carbamat
e (2d): light yellow solid, MP: 104 – 106 °C, 177.6 mg, yield: 76%; 1H NMR (CDCl3, 400 MHz)
δ: 8.05 (1 H, d, J = 7.8 Hz), 7.81 (1 H, d, J = 8.2 Hz), 7.67 (1 H, d, J = 8.0 Hz), 7.46 (2 H, p, J =
6.7 Hz), 7.36 (2 H, p, J = 7.1 Hz), 3.45 (2 H, d, J = 7.3 Hz), 3.33 – 3.02 (4 H, m), 1.98 (1 H, s),
1.62 – 1.26 (13 H, m), 1.11 (12 H, d, J = 19.7 Hz), 0.90 (3 H, s). 13C{1H}NMR (CDCl3, 100 MHz)
δ: 155.9, 134.0, 132.1, 128.7, 126.7, 126.5, 125.7, 125.4, 125.3, 124.1, 83.3, 79.1, 48.4, 46.7, 32.0,
29.8, 28.6, 24.9, 20.2, 13.9. TOF-HRMS Calcd. for C28H42BNO4Na [M+Na+]: 490.3104, found
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490.3102. 93% ee; [α]D = -9.7 (c = 1.0, CHCl3); HPLC condition: Lux 5μm Amylose-1 (250 ×
4.60 mm) (250 × 4.60 mm), ipa : hex = 2 : 98, 1.0 mL/min, 254 nm; tA = 3.8 min (minor), tB = 4.2
min (major).
tert-butyl
benzyl-(3-(naphthalen-1-yl)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-propyl)-carbama
1
te (2e): light yellow oil, 168.0 mg, yield: 67%; H NMR (CDCl3, 400 MHz) δ: 8.04 (1 H, d, J =
7.7 Hz), 7.91 – 7.83 (1 H, m), 7.79 (1 H, d, J = 8.2 Hz), 7.52 (3 H, t, J = 9.2 Hz), 7.44 (1 H, d, J =
7.5 Hz), 7.41 – 7.29 (5 H, m), 7.17 (1 H, d, J = 15.6 Hz), 6.17 (1 H, s), 4.58 (2 H, s), 4.10 (2 H, d,
J = 42.3 Hz), 1.54 (9 H, s). 13C{1H}NMR (CDCl3, 100 MHz) δ: 138.5, 134.7, 133.7, 131.2, 128.7,
128.0, 127.4, 126.1, 125.9, 125.7, 123.9, 80.1, 49.8, 48.7, 28.6, 27.0. TOF-HRMS Calcd. for
C31H41BNO4 [M+H+]: 502.3129, found 502.3132. 90% ee; [α]D20 = -3.25 (c = 1.0, CHCl3); HPLC
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condition: Lux 5μm Amylose-1 (250 × 4.60 mm) (250 × 4.60 mm), ipa : hex = 2 : 98, 1.0 mL/min,
254 nm; tA = 6.2 min (minor), tB = 7.0 min (major).
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allyl-(3-(naphthalen-1-yl)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-propyl)-carbamate
(2f): light yellow solid, MP: 100 – 102 °C, 151.2 mg, yield: 67%; 1H NMR (CDCl3, 400 MHz) δ:
8.04 (1 H, d, J = 8.1 Hz), 7.82 (1 H, d, J = 8.1 Hz), 7.67 (1 H, d, J = 7.8 Hz), 7.53 – 7.41 (2 H, m),
7.36 (2 H, p, J = 6.7 Hz), 5.78 (1 H, d, J = 20.0 Hz), 5.08 (2 H, s), 4.21 – 3.66 (2 H, m), 3.58 –
2.95 (4 H, m), 2.00 (1 H, d, J = 22.3 Hz), 1.50 – 1.33 (9 H, m), 1.11 (12 H, d, J = 18.4 Hz).
13C{1H}NMR (CDCl3, 100 MHz) δ: 155.8, 134.1, 133.9, 132.1, 128.8, 126.5 125.8, 125.4, 125.3,
124.1 118.1, 116.2 83.3 49.7, 32.0, 29.7 28.5, 24.9, 22.8, 14.2. TOF-HRMS Calcd. for
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C27H39BNO4 [M+H+]: 452.2972, found 452.2969. 90% ee; [α]D = -19.82 (c = 1.0, CHCl3);
HPLC condition: Lux 5μm Amylose-1 (250 × 4.60 mm) (250 × 4.60 mm), ipa : hex = 2 : 98, 1.0
mL/min, 254 nm; tA = 4.2 min (minor), tB = 4.6 min (major).
Compound 2g: light yellow solid, MP: 59 – 61 °C, 102.2 mg, yield: 40%; 1H NMR (CDCl3, 400
MHz) δ: 8.03 (1 H, d, J = 8.0 Hz), 7.83 – 7.77 (1 H, m), 7.66 (1 H, d, J = 8.1 Hz), 7.48 – 7.37 (3 H,
m), 7.35 – 7.28 (1 H, m), 3.82 (2 H, d, J = 7.8 Hz), 3.30 – 3.07 (2 H, m), 2.01 (1 H, q, J = 7.8 Hz),
1.46 (18 H, s), 1.09 (12 H, d, J = 20.2 Hz). 13C{1H}NMR (CDCl3, 100 MHz) δ: 153.0, 137.8,
134.0, 132.1, 128.7, 126.7, 126.6, 125.7, 125.3, 124.2, 83.3, 82.1, 48.0, 32.1, 28.2, 24.9.
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=
-14.39 (c = 1.0, CHCl3); HPLC condition: Lux 5μm Amylose-1 (250 × 4.60 mm) (250 × 4.60 mm),
ipa : hex = 2 : 98, 1.0 mL/min, 254 nm; tA = 3.6 min (minor), tB = 3.9 min (major).
tert-butyl
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methyl-(3-(naphthalen-2-yl)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-propyl)-carbam
ate (2h): light yellow solid, MP: 60 – 62 °C, 119.1 mg, yield: 56%; 1H NMR (CDCl3, 400 MHz) δ:
7.75 (3 H, dd, J = 16.7, 7.9 Hz), 7.64 (1 H, s), 7.45 – 7.30 (3 H, m), 3.46 – 3.20 (2 H, m), 2.86 –
2.79 (5 H, m), 1.86 (1 H, p, J = 8.2 Hz), 1.43 (9 H, s), 1.09 (12 H, d, J = 14.3 Hz). 13C{1H}NMR
(CDCl3, 100 MHz) δ: 156.1, 133.6, 132.1, 127.8, 127.6, 127.5, 126.9, 125.8, 125.1, 83.4, 35.1,
32.0, 29.8, 28.6, 24.9, 22.8, 14.2. TOF-HRMS Calcd. for C25H36BNO4Na [M+Na+]: 448.2634,
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found 448.2636. 88% ee; [α]D = -9.13 (c = 1.0, CHCl3); HPLC condition: Lux 5μm Amylose-1
(250 × 4.60 mm) (250 × 4.60 mm), ipa : hex = 2 : 98, 1.0 mL/min, 254 nm; tA = 5.5 min (minor),
tB = 6.2 min (major).
ethyl
methyl-(3-(naphthalen-1-yl)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-propyl)-carbam
ate (2i): light yellow oil, 178.8 mg, yield: 90%; 1H NMR (CDCl3, 400 MHz) δ: 8.10 (1 H, d, J =
7.8 Hz), 7.90 – 7.81 (1 H, m), 7.78 (1 H, d, J = 8.2 Hz), 7.58 (1 H, d, J = 7.1 Hz), 7.56 – 7.40 (3 H,
m), 7.24 (1 H, d, J = 15.3 Hz), 6.19 (1 H, s), 4.19 (4 H, dq, J = 22.8, 7.1 Hz), 2.99 (3 H, s), 1.31 (3
H, t, J =7.1 Hz). 13C{1H}NMR (CDCl3, 100 MHz) δ: 156.7, 134.5, 133.7, 131.2, 129.9, 128.7,
128.3, 128.1, 126.2, 125.9, 125.7, 124.1, 123.8, 100.0, 61.5, 51.1, 33.6, 14.9. TOF-HRMS Calcd.
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for C23H33BNO4 [M+H+]: 398.2501, found 398.2502. 94% ee; [α]D = -5.46 (c = 1.0, CHCl3);
HPLC condition: Lux 5μm Amylose-1 (250 × 4.60 mm) (250 × 4.60 mm), ipa : hex = 2 : 98, 1.0
mL/min, 254 nm; tA = 7.3 min (minor), tB = 7.9 min (major).
ethyl
methyl-(3-(naphthalen-2-yl)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-propyl)-carbam
ate (2j): light yellow oil, 115.2 mg, yield: 58%; 1H NMR (CDCl3, 400 MHz) δ: 8.02 (1 H, s), 7.81
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(1 H, d, J = 7.9 Hz), 7.67 (1 H, d, J = 7.9 Hz), 7.52 – 7.40 (2 H, m), 7.34 (2 H, q, J = 7.4, 5.6 Hz),
4.08 (2 H, dt, J = 16.6, 7.9 Hz), 3.61 – 3.26 (2 H, m), 3.15 (2 H, dd, J = 20.5, 8.3 Hz), 2.87 (3 H, d,
J = 39.0 Hz), 1.95 (1 H, t, J = 8.3 Hz), 1.25 (3 H, s), 1.11 (12 H, d, J = 18.2 Hz). 13C{1H}NMR
(CDCl3, 100 MHz) δ: 156.8, 134.0, 132.0, 128.8, 126.8, 126.5, 125.8, 125.4, 125.3, 124.0, 83.4,
61.2, 50.4, 33.8, 31.8, 29.8, 24.8, 22.8, 14.8. TOF-HRMS Calcd. for C23H33BNO4 [M+H+]:
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398.2501, found 398.2502. 90% ee; [α]D = -13.29 (c = 1.0, CHCl3); HPLC condition: Lux 5μm
Amylose-1 (250 × 4.60 mm) (250 × 4.60 mm), ipa : hex = 2 : 98, 1.0 mL/min, 254 nm; tA = 8.9
min (minor), tB = 9.9 min (major).
ethyl
(3-(6-methoxynaphthalen-2-yl)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-propyl)-(met
hyl)-carbamate (2k): light yellow solid, MP: 88 – 90 °C, 89.7 mg, yield: 42%; 1H NMR (CDCl3,
400 MHz) δ: 7.62 (2 H, d, J = 8.9 Hz), 7.56 (1 H, s), 7.09 (2 H, d, J = 8.8 Hz), 4.20 – 3.98 (2 H,
m), 3.89 (3 H, s), 3.56 – 3.24 (2 H, m), 3.01 – 2.68 (5 H, m), 1.85 (1 H, p, J = 8.1 Hz), 1.23 – 1.19
(3 H, m), 1.09 (12 H, d, J = 13.2 Hz). 13C{1H}NMR (CDCl3, 100 MHz) δ: 157.5, 133.1, 129.1,
128.9, 128.2, 126.8, 126.6, 118.6, 105.7, 83.4, 61.2, 55.3, 49.8, 34.8, 24.8, 14.8. TOF-HRMS
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Calcd. for C24H35BNO5 [M+H+]: 428.2607, found 428.2605. 90% ee; [α]D = -49.25 (c = 1.0,
CHCl3); HPLC condition: Lux 5μm Amylose-1 (250 × 4.60 mm) (250 × 4.60 mm), ipa : hex = 2 :
98, 1.0 mL/min, 254 nm; tA = 12.7 min (minor), tB = 15.5 min (major).
(3-(7-bromonaphthalen-2-yl)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propyl)(methyl)
carbamate (2l): light yellow oil, 221 mg, yield: 88%; 1H NMR (CDCl3, 400 MHz) δ: 7.88 (1 H, d,
J = 1.8 Hz), 7.68 (1 H, d, J = 8.4 Hz), 7.63 (1 H, d, J = 8.7 Hz), 7.54 (1 H, s), 7.45 (1 H, dd, J =
8.7, 1.9 Hz), 7.36 (1 H, d, J = 8.3 Hz), 3.57 – 3.09 (2 H, m), 2.83 (5 H, dd, J = 15.8, 7.8 Hz), 1.84
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