Enantioselective Dihydroxylation of Alkenes Catalyzed by 1,4-Bis(9-O-dihydroquinidinyl)phthalazine-Modified Binaphthyl–Osmium Nanoparticles

Article abstract of DOI:10.1002/cctc.201701368

A series of unprecedented binaphthyl–osmium nanoparticles (OsNPs) with chiral modifiers were applied in the heterogeneous asymmetric dihydroxylation of alkenes. A remarkable size effect of the OsNPs, depending on the density of the covalent organic shells, on the reactivity and enantioselectivity of the dihydroxylation reaction was revealed. Successful recycling of the OsNPs was also demonstrated and high reaction efficiency and enantioselectivity were maintained.

Full text of DOI:10.1002/cctc.201701368

Accepted Article
Title: Enantioselective Dihydroxylation of Alkenes Catalyzed by
(DHQD)2PHAL-Modified Binaphthyl-Osmium Nanoparticles
Authors: Jie Zhu, Xiao-Tao Sun, Xiao-Dong Wang, and Lei Wu
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: ChemCatChem 10.1002/cctc.201701368
Link to VoR: http://dx.doi.org/10.1002/cctc.201701368
A Journal of
www.chemcatchem.org

10.1002/cctc.201701368
ChemCatChem
COMMUNICATION
Enantioselective Dihydroxylation of Alkenes Catalyzed by
(DHQD)2PHAL-Modified Binaphthyl-Osmium Nanoparticles
Jie Zhu,[a] Xiao-Tao Sun,[a] Xiao-Dong Wang,[a] and Lei Wu*[a],[b]
Abstract:
A
series of unprecedented binaphthyl-osmium
applications
intermolecular
into
asymmetric
1,4-addition,
asymmetric
asymmetric
arylation,
nanoparticles (OsNPs) modified with chiral modifiers were applied in
the heterogeneous asymmetric dihydroxylation of alkenes.
Remarkable size effect of the OsNPs on the reactivity and
enantioselectivity of dihydroxylation was revealed depending on the
density of the covalent organic shells. Successful recycling of the
OsNPs was also demonstrated with high reaction efficiency and
enantioselectivity maintained.
cyclopropanation,
asymmetric transfer hydrogenation and asymmetric oxidation,
respectively.
Mechanistically, the challenge of using metal nanoparticles for
asymmetric catalysis lies in preventing the essential catalytic
species from leaching metal complexes during the reactions.[19]
Ligand-stabilized nano-catalysts are widely accepted as “semi-
heterogeneous” during the catalytic cycle, presenting
a
combination effect of nanoparticles and leaching metal
complexes. Thus, the development of unambiguous stabilization
during catalysis is an alternative central task. Intriguingly, in
2006, Mirhalaf et al. prepared the first metal-carbon bond-
stabilized gold and platinum nanoparticles, which exhibited
stronger bond energies than those of metal-nitrogen or metal-
sulfur bonds.[20a] Lately, the existence of carbon-metal covalent
bond on metal nanoparticles was evidenced by McDermott.[20b]
The heterogeneous catalytic applications of metal-carbon bond-
stabilized metal nanoparticles were further independently
investigated on hydrogenations, C-C bond formations and
oxidations, by Gopidas,[21] Sekar,[22] and our group.[23]
Nevertheless, to the best of our knowledge, this protocol has
never been applied to asymmetric catalysis. From our continuing
interest in nanocatalysis,[24] herein, we disclose the first
preparation of binaphthyl-stabilized osmium nanoparticles
(OsNPs) and their unprecedented investigations on the
asymmetric dihydroxylation (AD) of alkenes (Scheme 1c).
The application of metal nanoparticles in organic
transformations is one of the most important frontiers of
nanotechnology
in
recent
decades.[1]
Compared
to
homogeneous metal complexes or bulky metals, nanocatalysts
generally enable higher efficiencies and/or selectivities, largely
due to their large surface-to-volume ratios and the effects from
organic stabilizers.[2] Within this regime, a variety of organic
transformations, including C-C formation,[3] C-X formation,[4]
cyclization,[5] hydrogenation,[6] oxidation and others,[7] have been
achieved with metal nanoparticles as catalysts.
Notably, since the first report of rhodium-catalyzed
asymmetric hydrogenation in 1968 by Knowles,[8] asymmetric
catalysis utilizing nanocatalysts has gained extensive attention
by organic scientists. As pioneering contributions, Orito’s
platinum catalytic systems (cinchonidine-modified platinum
nanoparticles)[9] and tartaric acid-modified nickel nanoparticles[10]
have been widely recognized as versatile protocols for the
asymmetric hydrogenations of C=O bond. However, asymmetric
reactions catalyzed by metal nanoparticles were long restricted
to hydrogenation reactions until the current century. As depicted
in Scheme 1, in 2003, Fujihara revealed the first chiral BINAP-
stabilized palladium nanoparticles and their remarkable
enantioselectivity in the asymmetric hydrosilylation of olefins,[11]
and later in asymmetric Suzuiki-Miyaura coupling reactions.[12]
Chaudret and co-workers developed an enantioselective allylic
alkylation via a kinetic resolution catalyzed by chiral xylo-
furanoside diphosphite stabilized palladium nanoparticles.[13]
Notably, these developments evoked a hot research field since
2010. In addition to ligand stabilization, polymer-stabilized
nanoparticles, mainly benefiting from steric hindrance, have also
been developed for asymmetric reactions (Scheme 1b). Among
these studies, leading scientists, such as Kobayashi,[14] Toste,[15]
Glorius,[16] Morris,[17] and Hua,[18] have expanded the catalytic
Scheme 1. Representative studies on metal-nanoparticles catalyzed
asymmetric reactions since 2000 and this work.
[a]
[b]
Dr. J. Zhu, X.-T. Sun, X.-D. Wang and Prof. Dr. L. Wu
Jiangsu Key Laboratory of Pesticide Science and Department of
Chemistry, College of Sciences, Nanjing Agricultural University,
Nanjing 210095, P. R. China
E-mail: rickywu@njau.edu.cn
Prof. Dr. L. Wu
Beijing National Laboratory for Molecular Sciences and Institute of
Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R.
China
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
Asymmetric dihydroxylation of alkenes using catalytic amount
This article is protected by copyright. All rights reserved.

10.1002/cctc.201701368
ChemCatChem
COMMUNICATION
of Os(IV) and biscinchona alkaloids complexes provided the
most efficient approach to optical active vicinal diols.[25]
Nevertheless, the homogeneous protocol suffered from difficulty
in separating and recovering the toxic osmium catalyst. To
address these issues, several groups have devoted efforts to
immobilize the chiral ligands[26] or osmium onto various
supports[27]. However, recovery and recycle usage of the
osmium is still unsatisfied, and limited substrate scopes, poor
enantioselectivity and metal leaching were observed, dominantly
owing to the weak interaction of Os with supports. Most
importantly, metal nanoparticles have less been investigated in
AD. [18,28] We envisioned that the prevalent metal-carbon bond
stabilization might be an alternative approach to enable efficient
nanocatalytic asymmetric dihydroxylation.
In FT-IR spectra (Figure 2a), the lack of a diazonium band at
~2250 cm-1 and the aromatic C-N band between 1180 and 1360
cm-1 confirmed the complete removal of the diazonium group
after reduction, indicating the formation of covalent bonds
between osmium and carbon.[20] Thermogravimetric analysis
(TGA) curves were further recorded, which showed the high
thermal stability of the nanocatalysts up to 250 oC. Based on the
TGA data, the Os loading was calculated to be 5.3%, 7.1% and
13.8% for OsNPs-1, OsNPs-2, and OsNPs-3, respectively,
which were similar to the ICP results. X-ray photoelectron
spectroscropy (XPS) of OsNP-2 was then performed, showing a
weak Os signal at ~53.68 eV (Figure 2c). The weak intensity
was attributed to two aspects: the low Os content and, more
importantly, the encapsulation by the covalent organic shells for
stabilization. Although weak, the peak could be clearly
deconvoluted into two components: Os(0) 4f7/2 and 4f5/2 at 51.05,
53.84 eV; Os(III) 4f7/2 and 4f5/2 at 53.73 and 56.44 eV. [29] The
ratio between Os(III) and Os(0) was calculated to be
approximately 2:1, in good accordance with the stabilization of
surface Os by the organic shells through covalent bonds and the
unaltered core, which remained zero valent. EDS analysis for a
certain region was further carried out (in S.I.), which confirmed
the successful anchoring of Os component. The difference in Os
contents between EDS and ICP data could be attributed to two
aspects. Firstly, only a local content was reflected by EDS while
the ICP results denoted the whole material. Secondly and more
importantly, as Os was stabilized or nearly encapsulated by
organic shells through covalent bonds, the contents detected
from the surface should be much lower than the inner ones.
60
(a)
(c) 1.5± 0.8 nm
40
20
10 nm
0
80
60
40
20
0
1
2
3
(b)
1.5 ± 0.5 nm
(d)
10 nm
0
0
1
2
3
60
(c)
(e) 2.0 ± 0.5 nm
40
20
0
100
100
80
60
40
20
0
80
60
40
20
0
10 nm
0
1
2
3
Particle size (nm)
Figure 1. TEM images of (a) OsNPs-1; (b) OsNPs-2, and (c)
OsNPs-3 and the corresponding size distributions of (c) OsNPs-1,
OsNPs-1
OsNPs-2
OsNPs-3
(d) OsNPs-2, and (e) OsNPs-3
.
The study was initiated by the preparation of binaphthyl-
stabilized OsNPs with our previously reported “one-phase
reduction” procedure.[23] Three types of racemic pre-
nanocatalysts (OsNPs-1, OsNPs-2, and OsNPs-3) were
obtained by altering the ratio of the osmium precursor and
binaphthyl bis-diazonium salt (see details in the Supporting
Information). The resulting OsNPs were soluble in nonpolar
organic solvents, such as tetrahydrofuran, dichloromethane and
toluene, but insoluble in alcohols or water. The Os contents of
the synthesized nanoparticles were further determined by
inductively coupled plasma (ICP) as follows: OsNPs-1, 5.57%;
OsNPs-2, 7.89%; and OsNPs-3, 11.76%. Transmission electron
microscopy (TEM) images and the corresponding size
distributions of the pre-catalysts revealed that no considerable
formation of aggregates was observed for each catalyst. The
pre-catalysts exhibited size distributions of 1.5±0.8 nm, 1.5±0.5
nm and 2.0±0.5 nm for OsNPs-1, OsNPs-2 and OsNPs-3,
respectively. Notably, higher contents of the covalent organic
shell led to smaller catalyst particle size but inhomogeneous
distribution (Figure 1a, OsNPs-1). On the other hand, using less
covalent organic shell, the particles grew larger owing to
"Ostwald ripening" without the additional passivation (Figure 1c,
OsNPs-3).
200 400 600 800 1000
Temperature(oC)
4000 3000 2000 1000
Wavenumber (cm-1)
100
80
60
40
20
0
OsNPs-2
OsCl3
40
50
60
70
0
5
10 15 20 25 30
Reaction time (h)
Binding energy (ev)
Figure 2. FT-IR (a); TGA (b); XPS of OsNPs (c); comparison of
the reaction progress catalyzed by OsNPs-2 and OsCl3 (d).
With the pre-catalyst OsNPs in hand, initial attempts to
perform the Sharpless AD of styrene were conducted in a
H2O2-acetone/H2O system. In the presence of 1,4-bis(9-O-
[25]
dihydroquinidinyl)phthalazine ((DHQD)2PHAL, L1
)
as a
chiral ligand, over 90% yield of vicinal diol was obtained at
room temperature. However, unsatisfactory ee values were
afforded (Table 1, entry 1). Tert-butylhydroperoxide was
further tested but still gave poor enantiomeric selectivity
with only 16.4% ee (entry 2, full screening results are
available in the S.I.). To our delight, using K3Fe(CN)6 and
This article is protected by copyright. All rights reserved.

10.1002/cctc.201701368
ChemCatChem
COMMUNICATION
K2CO3 as additives, the ee value was greatly improved to
84.5%, giving the R-enantiomer of 2a in 94% yield (entry 3).
Afterwards, the solvents proved to play key roles in this
system regarding both the yields and ee values. Various
solvents, including mixed solvents with different proportions
were tested, among which BuOH/H2O(1:1) exhibited
amazing ee values and a high yield of 98% (entries 4-6).
Further optimizations confirmed that (DHQD)2PHAL was the
best chiral ligand. More importantly, among the three
[a] Reaction conditions: styrene (0.5 mmol), solvent (2 mL), OsNPs-2 (5 mg, 0.4
mol%), ligand (1 mol%), K3Fe(CN)6 (2 equiv), K2CO3 (1 equiv), 6 h; isolated
[b]
yields; ee values were determined with an OD-H column on HPLC; H2O2 was
[c]
used instead of K3Fe(CN)6 and K2CO3; TBHP was used instead of K3Fe(CN)6
and K2CO3; [d] [Os(IV)]= K2OsO4·2H2O/binaphthyl bis-diazonium salt (1:1).
Table 2. Substrate scope of alkenes.[a]
osmium nanocatalysts, OsNPs-2
,
with
a
moderate
metal/racemic ligand ratio, was shown to provide the best
performance. Considering the TEM results, it was
suggested that appropriate amount of binaphthyl groups is
necessary to stabilize the metal nanoparticles, while
maintaining spontaneous access of substrates and chiral
ligands. However, excessive binaphthyl groups may
saturate the active sites against the coordination of
substrates and chiral ligands on the particle surface. Hence,
OsNPs-2 was utilized for further investigations as a racemic
pre-nanocatalyst. Considering the components of OsNPs-2
,
a mixture of Os(III) and Os(0) species, the reaction
progress data for OsNPs-2 and OsCl3 were compared in
Figure 2d under the optimal conditions. The AD proceeded
considerably slower in the homogeneous OsCl3 system,
requiring approximately 21 hours for complete consumption
of styrene, albeit with an ee value of 94.5%. In
contrast, >95% of styrene was consumed within 5 hours
with the heterogeneous OsNPs-2. Moreover, Os(0) black,
potassium osmate dihydrate (Sharpless AD reagent), and a
potassium osmate dihydrate/binaphthyl bis-diazonium salt
combination were also used as comparison, which all gave
either worse yields or enantiocontrol (Table 1, entry 10-12).
Thus, OsNPs-2 exhibited considerable enhancements of
the activity and enantiocontrol. The results indicated that
the enhanced reaction rate might be attributed to the shell
effect and the highly dispersed nature of the OsNPs.
[a] Reaction conditions: styrene (0.5 mmol), solvent (2 mL), OsNPs-2 (5 mg,
0.4 mol%), ligand (1 mol%), K3Fe(CN)6 (2 equiv), K2CO3 (1 equiv), 6 h;
isolated yields; ee values were determined with an OD-H column on HPLC.
Table 1. Optimization of the Reaction Conditions.[a]
The successful AD with OsNPs prompted us to examine the
generality of this protocol for various substituted alkenes, as
summarized in Table 2. In addition to styrene, other terminal
alkenes, 1-phenyl butene and t-butyl acrylate, also performed
well, leading to good ee values of 74.9% and 75.3%, respectively,
together with good yields (2b-2c). Styrenes bearing different
substituents on benzene ring (p-methyl, p-chloro and m-chloro)
smoothly proceeded in the system (2d-2f), affording R-
enantiomers in excellent yields and ee values (98.0-99.3%).
Notably, the dihydroxylation of trans-β-methylstyrene and cis-β-
methylstyrene was compared (2g and 2h). Trans-β-methylstyrene
mainly gave the syn-adduct (1R, 2R) with 93% yield and 97.1%
ee. Similarly, in the reaction of cis-β-methylstyrene, the syn-
adduct (1R, 2S) was isolated in 81% yield and 96.5% ee. The
results suggested a Si-attack process from the C1 position in this
system.[18] Cinnamates, including those with methyl ester, ethyl
ester and isopropyl ester groups, performed well in the system,
displaying excellent ee values of over 98% (2i-2k). When the
entry
catalyst
solvent
yield/e.e.(%)
1b
2c
OsNPs-2
OsNPs-2
acetone/H2O(1:1)
acetone/H2O(1:1)
92/3.3
92/16.4
3
OsNPs-2
acetone/H2O(1:1)
94/84.5
4
OsNPs-2
OsNPs-2
OsNPs-2
OsNPs-1
OsNPs-3
OsCl3
Os0 black
K2OsO4·2H2O
[Os(IV)]d
CH3OH/H2O(9:1)
CH3OH/H2O(1:9)
t-BuOH/H2O(1:1)
t-BuOH/H2O(1:1)
t-BuOH/H2O(1:1)
t-BuOH/H2O(1:1)
t-BuOH/H2O(1:1)
t-BuOH/H2O(1:1)
t-BuOH/H2O(1:1)
33/3.5
5
41/60.7
98/98.1
trace/-
6
7
8
88/85.3
32/94.5
30/81.3
65/96.8
25/16
9
10
11
12
This article is protected by copyright. All rights reserved.

10.1002/cctc.201701368
ChemCatChem
COMMUNICATION
[1] a) D. Astruc, nanoparticles and catalysis, Wiley-VCH, 2008; b) L. S. Ott, R.
G. Finke, Coord. Chem. Rev. 2007, 251, 1075; c) V. Polshettiwar, R. S.
Varma, Green Chem. 2010, 12, 743; d) A. M. Molenbroek, S. Helveg, H.
Topsøe, B. S. Clausen, Top. Catal. 2009, 52, 1303; e) D. Wang, D. Astruc,
Chem. Soc. Rev. 2017, 46, 816.
ester group was changed to an amide, the enantioselectivity
remained high, but the yield slightly decreased (2l). For other
disubstituted alkenes, such as 1-phenl-3-bromopropene, trans-
stilbene and dimethyl maleate (2m-2o), the yields and ee were
good to excellent. Several cyclic alkenes, including 1-phenyl
cyclohexene, indene and 1,2-dihydro-naphthalene, were also
tested, giving 14.4-96.8% ee values (2p-2r). However, alkenes
with strong electron-withdrawing groups, such as –CN and –NO2,
failed to give the corresponding products (2s and 2t). The above
results are somehow complementary to the FeII(L)(OTf)2 system
recently reported by Che et al.,[30] in which higher ee values were
obtained for cyclic alkenes, and β-methylstyrene, 1-phenl-3-
bromo-propene and some others provided unsatisfactory results.
The opposite cases were observed in this work.
In addition to high efficiency and enantiomeric selectivity,
further experiments were conducted to determine the essential
catalytic species. A Hg poisoning experiment, together with hot
filtration, verified the heterogeneous nature of the catalysis (see
details in the S.I.). The heterogeneous osmium catalyst also
showed superiority in its recovery and reusability. The recovered
catalyst could be recycled at least 5 times in the AD of styrene
without obvious loss of activity or enantioselectivity, displaying a
high level on the 5th cycle (96.3%). Hence, the osmium
nanocatalyst solves some major problems associated with
homogeneous osmium catalytic systems, such as difficulty in
recovery and product contamination. Usually, Os precursors are
immobilized via molecular interactions with the support materials,
in which the weak interactions can easily be broken,[31] leading
to the Os leaching into reaction solution. The TEM image of the
recovered OsNPs (5th cycle, 1.6±0.5 nm, S.I.), and the ICP data
for OsNPs-2 before the reaction (7.89%) and after the 5th cycle
(7.86%) collectively showed that nearly no leaching occurred
during the hydroxylation process, confirming the outstanding
stability of the nanocatalyst stabilized by C-Os covalent bonds.
[2] a) G. Schmid, Clusters and Colloids, VCH: Weinheim, 1994; b) D. L.
Feldheim, Jr. C. A. Foss, Metal Nanoparticles, Marcel Dekker: New York,
2002.
[3] a) A. Roucoux, J. Schulz, H. Patin, Chem. Rev. 2002, 102, 3757; b) L. Wu,
B.-L. Li, Y.-Y. Huang, H.-F. Zhou, Y.-M. He, Q.-H. Fan, Org.
Lett. 2006, 8, 3605; c) H. Cao, H. Jiang, G. Yuan, Z. Chen, C. Qi, H.
Huang, Chem. Eur. J. 2010, 16, 10553.
[4] a) M. Gholinejad, N. Jeddi, ACS Sustainable Chem. Eng. 2014, 2, 2658; b)
M. D’Halluin, T. Mabit, N. Fairley, V. Fernandez, M. B. Gawande, E. L.
Grognec, F.-X. Felpin, Carbon, 2015, 93, 974; c) J. Oliver-Messeguer, L.
Liu, S. García-García, C. Canós-Giménez, I. Domínguez, R. Gavara, A.
Doménech-Carbó, P. Concepción, A. Leyva-Pérez and A. Corma, J. Am.
Chem. Soc., 2015, 137, 3894–3900
[5] a) M. Kaur, S. Pramanik, M. Kumar, V. Bhalla, ACS Catal. 2017, 7, 2007;
b) R. Gupta, P. K. Sahua, P. K. Sahub, S. K. Srivastavaa, D. D. Agarwal,
Catal. Commun. 2017, 92, 119; c) D. K. Tiwari, J. Pogula, B. Sridhar, D. K.
Tiwari, P. R. Likhar, Chem. Commun. 2015, 51, 13646.
[6] a) L. Wu, Y. Zhang, Y.-G. Ji, Curr. Org. Chem. 2013, 17, 1288; b) L. Wu,
Z.-W. Li, F. Zhang, Y.-M. He, Q.-H. Fan, Adv. Synth. Catal. 2008, 350,
846; c) H. Park, D. A. Reddy, Y. Kim, S. Lee, R. Ma, M. Lim, T. K. Kim,
Appl. Surf. Sci. 2017, 401, 314.
[7] a) G. Zhao, M. Ling, H. Hu, M. Deng, Q. Xue, Y. Lu, Green Chem. 2011,
13, 3088; b) H. Wang, W. Fan, Y. He, J. Wang, J. N. Kondo, T. Tatsumi, J.
Catal. 2013, 299, 10.
[8] W. S. Knowles, Acc. Chem. Res. 1983, 16, 106.
[9] a) Y. Orito, S. Imai, S. Niva, J. Chem. Soc. Jpn. 1979, 1118; b) M. Bartók,
K. Felföldi, G. Szöllösi, T. Bartók, Catal. Lett. 1999, 61, 1.
[10] a) T. Harada, Y. Izumi, Chem. Lett. 1978, 1195; b) Y. Orito, S. Niwa, S.
Imai, J. Syn. Org. Chem., Jpn, 1976, 34, 236.
[11] M. Tamura, H. Fujihara, J. Am. Chem. Soc. 2003, 125, 15742.
[12] K. Sawai, R. Tatumi, T. Nakahodo, H. Fujihara, Angew. Chem., Int. Ed.
2008, 47, 6917.
[13] S. Jansat, M. Gómez, K. Philippot, G. Muller, E. Guiu, C. Claver, S.
Castillón, B. Chaudret, J. Am. Chem. Soc. 2004, 126, 1592.
[14] a) T. Yasukawa, H. Miyamura, S. Kobayashi, J. Am. Chem. Soc. 2012,
134, 16963; b) T. Yasukawa, A. Suzuki, H. Miyamura, K. Nishino, S.
Kobayashi, J. Am. Chem. Soc. 2015, 137, 6616; c) T. Yasukawa, Y.
Saito, H. Miyamura, S. Kobayashi, Angew. Chem., Int. Ed. 2016, 55,
8058.
In summary, we revealed an unprecedented example of AD
of alkenes catalyzed by binaphthyl-osmium nanocatalyst with
(DHQD)2PHAL as a chiral modifier. Remarkable reactivity and
enantioselectivity dependent on the size and shell effect of the
OsNPs were revealed while altering the ratio of osmium
precursor and bis-diazonium salt. The reaction tolerated various
functional groups, including halogens, phenyls, alicycles, amides
and esters, furnishing the diol products in good to excellent
yields and ee values under mild conditions. In addition, the het-
erogeneous nanocatalyst could be recycled for at least 5 times
without obvious loss of activity or enantioselectivity.
[15] E. Gross, J. H. Liu, S. Alayoglu, M. A. Marcus, S. C. Fakra, F. D. Toste,
G. A. Somorjai, J. Am. Chem. Soc. 2013, 135, 3881.
[16] K. V. S. Ranganath, J. Kloesges, A. H. Schäfer, F. Glorius, Angew.
Chem., Int. Ed. 2010, 49, 7786.
[17] a) A. Mikhailine, A. J. Lough, R. H. Morris, J. Am. Chem. Soc. 2009, 131,
1394; b) J. F. Sonnenberg, N. Coombs, P. A. Dube, R. H. Morris, J. Am.
Chem. Soc. 2012, 134, 5893.
[18] B. Hao, M. J. Gunaratna, M. Zhang, S. Weerasekara, S. N. Seiwald, V.
T. Nguyen, A. Meier, D. H. Hua, J. Am. Chem. Soc. 2016, 138, 16839.
[19] a) S. Kobayashi, M. Sugiura, Adv. Synth. Catal. 2006, 348, 1496; b) C.
Deraedt, D. Astruc, Acc. Chem. Res. 2014, 47, 494.
Acknowledgements ((optional))
[20] a) F. Mirkhalaf, J. Paprotny, D. J. Schiffrin, J. Am. Chem. Soc. 2006, 128,
7400; b) L. Laurentius, S. R. Stoyanov, S. Gusarov, A. Kovalenko, R. Du,
G. P. Lopinski, M. T. McDermott, ACS Nano, 2011, 5, 4219.
[21] V. K. R. Kumar, K. R. Gopidas, Tetrahedron Lett. 2011, 52, 3102.
[22] a) D. Ganapathy, G. Sekar, Org. Lett. 2014, 16, 3856; b) D. Ganapathy,
G. Sekar, Catal. Commun. 2013, 39, 50; c) S. S. Kotha, N. Sharma, G.
Sekar, Adv. Synth. Catal. 2016, 358, 1694.
We are grateful for financial support from the National Natural
Science Foundation of China (NSFC, Grant No. 21372118,
21602108).
Keywords: binaphthyl-osmium nanoparticles • covalent carbon-
metal bond • asymmetric dihydroxylation • alkenes • chiral
modification
[23] a) Y. Zhang, J. Zhu, Y.-T. Xia, X.-T. Sun, L. Wu, Adv. Synth. Catal. 2016,
358, 3039; b) X.-T. Sun, J. Zhu, Y.-T. Xia, L. Wu, ChemCatChem, 2017,
9, 2463; c) Y. Zhang, M. Mao, Y.-G. Ji, J. Zhu, L. Wu, Tetrahedron Lett.
2016, 57, 329.
This article is protected by copyright. All rights reserved.

10.1002/cctc.201701368
ChemCatChem
COMMUNICATION
[24] a) L. Wu, X. Zhang, Z. Tao, Catal. Sci. Technol. 2012, 2, 707; b) Y.-G.
Ji, K. Wei, T. Liu, L. Wu, W.-H. Zhang, Adv. Synth. Catal. 2017, 359,
933.
Jyothi, M. L. Kantam, J. Am. Chem. Soc. 2002, 124, 5341; c) R. Akiyama,
S. Kobayashi, Chem. Rev. 2009, 109, 594; d) R. Akiyama, N. Matsuki, H.
Nomura, H. Yoshida, T. Yoshida, S. Kobayashi, RSC Adv. 2012, 2, 7456;
e) N. Shilpa, J. Manna, R. K. Rana, Eur. J. Inorg. Chem. 2015, 4965.
[28] For non-asymmetric dihydroxylation catalyzed by metal nanoparticles,
Osmium: Ö. Metin, N. A. Alp, S. Akbayrak, A. Biçer, M. S. Gültekin, S.
Özkar, U. Bozkaya, Green Chem. 2012, 14, 1488; Ruthenium: C.-M. Ho,
W.-Y. Yu, C.-M. Che, Angew. Chem. Int. Ed. 2004, 43, 3303.
[25] a) J. R. Coombs, J. P. Morken, Angew. Chem. Int. Ed. 2016, 55, 2636; b)
H. Srour, P. L. Maux, S. Chevance, G. Simonneaux, Coord. Chem. Rev.
2013, 257, 3030; c) H. C. Kolb, M. S. VanNieuwenhze, K. B. Sharpless,
Chem. Rev. 1994, 94, 2483; d) H. Becker, K. B. Sharpless, Angew.
Chem. Int. Ed. 1996, 35, 448.
[26] For selected examples: a) H. Li, Y.-Y. Luk, M. Mrksich, Langmuir, 1999,
15, 4957; b) I. Motorina, C. M. Crudden, Org. Lett., 2001, 3, 2325; c) B.
M. Choudary, N. S. Chowdari, K. Jyothi, N. S. Kumar, M. L. Kantam,
Chem. Commun., 2002, 586; d) S. Kobayashi and M. Sugiura, Adv.
Synth. Catal. 2006, 348, 1496.
[29] a) C. J. Powell, Appl. Surf. Sci. 1995, 89, 141; b) A. Pitto-Barry, L. M. A.
Perdigao, M. Walker, J. Lawrence, G. Costantini, P. J. Sadler, N. P. E.
Barry, Dalton Trans. 2015, 44, 20308.
[30] C. Zang, Y. Liu, Z.-J. Xu, C.-W. Tse, X. Guan, J. Wei, J.-S. Huang, C.-M.
Che, Angew. Chem., Int. Ed. 2016, 55, 10253.
[27] For selected examples: a) S. Kobayashi, M. Endo, S. Nagayama, J. Am.
Chem. Soc. 1999, 121, 11229; b) B. M. Choudary, N. S. Chowdari, K.
[31] S. Kobayashi, M. Sugiura, Adv. Synth. Catal. 2006, 348, 1496.
This article is protected by copyright. All rights reserved.

10.1002/cctc.201701368
ChemCatChem
COMMUNICATION
COMMUNICATION
Jie Zhu, Xiao-Tao Sun, Xiao-Dong
Wang, Lei Wu*
100
80
60
40
20
0
Yield
—— ee value
Page No. – Page No.
Enantioselective Dihydroxylation of
Alkenes Catalyzed by (DHQD)2PHAL-
Modified Binaphthyl-Osmium
Nanoparticles
Binaphthyl-Osmium Nanoparticles: The first enantioselective dihydroxylation of
alkenes was achieved by a novel (DHQD)2PHAL-modified Binaphthyl-Osmium
nanoparticles, with demonstration of shell density effect and recyclability.
This article is protected by copyright. All rights reserved.