New mono- and bidentate P-ligands using one-pot click-chemistry: Synthesis and application in Rh-catalyzed hydroformylation

Article abstract of DOI:10.1016/j.tet.2013.07.070

Three families of new phosphorus ligands have been prepared using the click-chemistry approach proceeding in only two steps and without intermediate P-protection. The methodology allows the high yield production of mono- and bidentate P-ligands, bearing at least one P-O bond. The ligands were tested in the Rh-catalyzed hydroformylation of 1-octene.

Full text of DOI:10.1016/j.tet.2013.07.070

Accepted Manuscript
New Mono- and Bidentate P-Ligands Using One-pot Click-Chemistry: Synthesis and
Application in Rh-Catalyzed Hydroformylation
Natalia V. Dubrovina, Lutz Domke, Ivan A. Shuklov, Anke Spannenberg, Robert
Franke, Alexander Villinger, Armin Börner
PII:
S0040-4020(13)01189-7
10.1016/j.tet.2013.07.070
TET 24652
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 5 June 2013
Revised Date: 17 July 2013
Accepted Date: 18 July 2013
Please cite this article as: Dubrovina NV, Domke L, Shuklov IA, Spannenberg A, Franke R, Villinger
A, Börner A, New Mono- and Bidentate P-Ligands Using One-pot Click-Chemistry: Synthesis and
Application in Rh-Catalyzed Hydroformylation, Tetrahedron (2013), doi: 10.1016/j.tet.2013.07.070.
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Graphical Abstract
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New Mono- and Bidentate P-Ligands Using
One-pot Click-Chemistry: Synthesis and
Application in Rh-Catalyzed
Leave this area blank for abstract info.
Hydroformylation
Natalia V. Dubrovina*, Lutz Domke, Ivan A. Shuklov, Anke Spannenberg, Robert Franke, Alexander Villinger,
Armin Börner*
3
R2
R1-Br
OPR2
NaN3
+
2 steps
R2 = H, PAr2
R3 = Ar,OAr
N
N
R1
N
OH

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1
Tetrahedron
journal homepage: www.elsevier.com
New Mono- and Bidentate P-Ligands Using One-pot Click-Chemistry: Synthesis
and Application in Rh-Catalyzed Hydroformylation
Natalia V. Dubrovinaa , Lutz Domkea, Ivan A. Shuklovb, Anke Spannenbergb, Robert Frankec, Alexander
Villingera and Armin Börnera,b
aInstitut für Chemie der Universität Rostock, Albert-Einstein-St. 3a, 18059 Rostock, Germany.
bLeibniz-Institut für Katalyse an der Universität Rostock e.V., Albert-Einstein-St. 29a, 18059 Rostock, Germany.
cEvonik Industries GmbH, Paul-Baumann-Str. 1, 45 772 Marl, Germany.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
Three families of new phosphorus ligands have been prepared using the click-chemistry
approach proceeding in only two steps and without intermediate P-protection. The methodology
allows the high yield production of mono- and bidentate P-ligands, bearing at least one P-O
bond. The ligands were tested in the Rh-catalyzed hydroformylation of 1-octene.
Available online
Keywords:
click chemistry
2009 Elsevier Ltd. All rights reserved.
cycloaddition
phosphorus ligands
multicomponent reactions
hydroformylation
———
Corresponding author. Tel.: +49 381 498 6439; e-mail: natalia.dubrovina@uni-rostock.de
Corresponding author. Tel.: +49 381 1281 202; fax: +49 381 1281 51202; e-mail: armin.boerner@catalysis.de

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2
Tetrahedron
1. Introduction
dialkylphosphines also other potentially ligating groups, like 2-
pyridyl or alkylthio could be linked to the triazole. Kann and co-
workers employed click chemistry for the preparation of a library
of more than 20 P-chirogenic BH3 protected mono-phosphines.8
Matano and colleagues synthesized three α-(1-aryl-1,2,3-triazole-
4-yl)phospholes and used them in a study of the optical
properties of corresponding Pd and Pt complexes.9 Phospholes
were synthesized via their corresponding phosphine oxides, this
approach required final deoxygenation with HSiCl3.
Trivalent phosphorus compounds play a pivotal role as
ancillary ligands in transition metal catalysis.1 Subtle differences
in their electronic or steric properties may have a dramatic impact
on the catalytic features of the resulting metal catalyst. Synthetic
approaches which allow the preparation of large sets of strongly
related ligands are therefore particularly interesting. Usually for
the aim of variation a fixed organic scaffold is chosen and
phosphorus units bearing varying substituents are linked to it.
The modification of the scaffold would provide additional
possibilities of variation provided that modular and easy to
perform protocols are available.
Interestingly only a very few P-O-ligands have been synthesized
by this methodology. Thus, Zhang and Takacs prepared six
diphosphites used as macrocycle forming ligands in the Rh-
catalyzed asymmetric hydrogenation.10,11 A main advantage, the
introduction of the P-unit could be accomplished in the last step
by simple esterification of the phenolic hydroxyl groups.
Of particular value in this connectivity is the concept of
“click-chemistry” suggested by Sharpless and co-workers in
2001.2 The Cu(I)-catalyzed addition of organic azides to terminal
acetylenes (CuAAC reaction) leading to 1,4-disubstituted 1,2,3-
triazoles is one of the most representative examples.3 Moreover,
the reaction is nearly perfect in terms of atom economy and
selectivity. It gives high yields and can produce compounds in a
large diversity within a short time period. Therefore, it is not
astonishing that for the purpose of ligand synthesis click
chemistry has been already applied.
Therefore in contrast to other venues
a
tedious P-
protection/deprotection procedure is not required. Moreover, for
some catalytic applications ligands with strong π-accepting P-O-
groups are more efficient than phosphines. A typical example
concerns the Rh-catalyzed hydroformylation, where in particular
phosphites are first choice as ligands due to the strong π-
accepting properties.12
As a part of our ongoing studies concerned with the synthesis
of chiral13 and achiral phosphorus ligands,14 herein we will show,
that click-chemistry can be used for the preparation of numerous
electron deficient ligands bearing at least one P-O bond, namely
phosphinites and phosphites. A common feature of our protocol
consists in the assembling of hydroxymethyl substituted 1,2,3-
triazole derivatives by a simple Cu(I) catalyzed one-pot reaction
avoiding any organic azide in the first step followed by a
phosphorylation reaction in the second, final step. Besides
monodentate ligands of type A also bidentate hybrid ligands of
type B ligands can be derived from this approach. Quasi-
symmetric bidentate ligands with the same P-units (C) have been
produced by a related strategy.
Thus, Zhang assembled ca. 10 phosphine ligands abbreviated
as Clickphos on a 1,2,3-triazole backbone for Pd-catalyzed
amination or Suzuki-Miyaura coupling reaction (Figure 1).4 The
P-unit was connected to the heterocycle in the last step of the
synthetic sequence.
To show the usefulness of the new ligands they were investigated
in preliminary trials in the Rh-catalyzed hydroformylation of 1-
octene.
Figure 1. Phosphorus compounds useful for the application as
ligands produced by click-chemistry.
2. Results and Discussion
Up to now, most P-ligands prepared by click-chemistry were
assembled starting with organic azides. The latter are sometimes
difficult to handle in particular when low weight organic azides
have to be used. Therefore, we tried an alternative and safer
approach. Commercially available and cheap propargyl alcohol
was used as starting material. The in situ Cu(I)-catalyzed reaction
was performed by a modification of the approach of Fokin and
co-workers.15
Later on, Fukuzawa and co-workers prepared the first bidentate
diphosphine ligands, called ClickFerrophos, by
a similar
pathway.5 In contrast for the synthesis of Clickphine ligands,
Reek and van Maarseveen subjected propinyldiphenylphosphine
to the cyclization reaction.6 This approach required the protection
of the trivalent phosphorus as BH3 adduct. Both phosphine
groups were incorporated in the last step. Due to the different
reactivity of ferrocenyl and triazole unit even the introduction of
two different PAr2 groups became possible. The two ligands
derived were tested for asymmetric hydrogenation and allylic
substitution, respectively. Pincer-ligands for the Heck reaction
were constructed by Gandelman’s group by reaction of
phosphinylmethyl azides with propinylphosphines.7 Also in this
strategy the protection of the phosphine groups by BH3 or as
phosphine oxide, respectively, was indispensable in each case.
By extension of this methodology besides diaryl- or
Sodium azide and the corresponding alkyl bromides were reacted
in the presence of copper(II) to give the corresponding organic
azides, which in turn reacted without isolation with propargylic
alcohol to afford 4-hydroxymethyl substituted 1,2,3-triazoles 1a-f
in good yields (Table 1). It is noteworthy, that under these
smooth conditions also a 1,2,3-triazole bearing in 1-position a
non-benzylic sterically demanding substituent, such as 1-
cyclohexyl-4-(diphenylphosphinoxymethyl)-1H-1,2,3-triazole

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3
(1f) could be prepared although the product could be isolated
Table 2. Synthesis of monodentate P-ligands 2a-h.
only in a moderate yield. Alcohols 1a-f were characterized by 1H,
13C and – in the case of 1d,e - also using 19F NMR spectroscopy
as well as mass spectrometry. All products are crystalline and
were purified in a single crystallization step.
Table 1. Copper-catalyzed synthesis of 4-hydroxymethyl
substituted 1,2,3-triazoles
Product
2a
R1
(OR3)2
Yield
98
Bn
-
2b
4-Me-C6H4CH2
4-F-C6H4CH2
4-CF3-C6H4CH2
3-F-C6H4CH2
cHex
-
98
2c
-
99
2d
-
>99
>99
>99
93
2e
-
Product
1a
R1
Yield [%]
2f
-
Bn
73
93
88
94
82
39
2g
4-Me-C6H4CH2
4-F-C6H4CH2
(R)-Binaphthoxy
(R)-Binaphthoxy
1b
4-Me-C6H4CH2
4-F-C6H4CH2
4-CF3-C6H4CH2
3-F-C6H4CH2
cHex
1c
2h
96
1d
1e
1f
2.2 Synthesis of bidentate hybrid ligands (Type B)
The success of our methodology for the synthesis of
monodentate P-ligands prompted us also to test it in the synthesis
of bidentate P-ligands via lithiation of the triazole unit as
illustrated in Table 3. In our first trials, triazoles 1a-c were
treated with two equivalents of n-BuLi. We were pleased to see
that besides the hydroxyl group also the proton of the 1,2,3-
triazole is sufficiently acidic and can be removed. Upon reaction
with iodine and subsequent addition of water iodides 3a,b could
be isolated in good yields (up to 83 %) as crystalline materials by
a single recrystallization from ethyl acetate.
The structure of 1,2,3-triazole 1f was additionally analyzed by
X-ray structural analysis. Suitable crystals were obtained by
crystallization from dichloromethane/n-heptane. The solid-state
structure of 1-cyclohexyl-4-(hydroxymethylmethyl)-1H-1,2,3-
triazole (1f) is depicted in Figure 2 and confirms the expected
molecular structure.
Table 3. Synthesis of bidentate ligands 5a-d via dilithiation of
1,2,3-triazoles 1a-c.
1. 2 eq n-BuLi
2. I2/H2O
OH
OH
Figure 2. ORTEP diagram of triazole 1f, top view. The thermal
I
ellipsoids correspond to 30 % probability
N
N
R1
N
N
R1
N
N
1a-c
3a,b
2.1 Synthesis of monodentate phosphinite and phosphite
ligands (Type A)
1. 2 eq. n-BuLi
X
2 eq. n-BuLi
2. 2 eq. Ph2PCl
In the next step 4-hydroxymethyl-1,2,3-triazoles 1a-f were
converted selectively into the corresponding phosphinites 2a-f.
Lithiation of the alcohols using one equivalent of n-BuLi,
followed by addition of one equivalent ClPPh2 gave the desired
phosphinites in nearly quantitative yields (Table 2). Moreover,
we found that (R)-binaphthophosphochloridite which yields in a
prior esterification of (R)-binaphthol with PCl3 also reacts with
the intermediate Li-alcoholates to give phosphites 2g,h.
OLi
N
Li
OPR2
PR2
2
2
2 eq R22PCl
N
R1
N
N
R1
N
N
4a-c
5a-d
Product
5a
R1
Bn
R2
Yield
98
Ph
Ph
5b
4-Me-C6H4CH2
4-Me-C6H4CH2
4-F-C6H4CH2
98
5c
3,5-(CF3)2-C6H4CH2
Ph
95
5d
97
Crystals of iodide 3b were analyzed by X-ray crystallography
which confirmed the expected structure (Figure 3).

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4
Tetrahedron
In the next approach, we tried to synthesize bidentate P,P-
Table 4. Synthesis of bidentate diphosphite ligands from 2-
ligands by treatment of iodide 3a,b by double phosphorylation
with chlorophosphines. Unfortunately, all attempts to react the
iodides with two equivalents of n-BuLi and subsequent C-P-
coupling with Ph2PCl failed. Prolongation of the reaction time
and enhancement of the temperature gave an inseparable mixture
of products.
butyne-1,4-diol (6).
As an alternative synthetic approach we envisaged the direct
phosphorylation of the dilithium salts 4a-c by treatment with two
equivalents of Ar2PCl which afforded the desired phosphino-
phosphinites 5a-d in nearly quantitative yields (Table 3).
Unfortunately, the reaction with an excess of (R)-
binaphthophosphochloridite was not successful, probably the
linkage of this phosphonite group to the triazole moiety is not
favored due to steric hindrance.
Product
8a
R
Yield [%]
Ph
99
97
96
8b
(R)-Binaphthoxy
3,5-(CF3)2-C6H4CH2
8c
The possibility of ligands of type 8 to chelate to metals was again
proven by formation of the corresponding Pt-complexes. In the
31P NMR spectra of PtCl2(8a or 8b) the cis-chelation was
confirmed by two doublets of pseudotriplets at δ 87.06 (dd, 1J(P-Pt)
= 4187.9, 2J(P-P) = 7.4 Hz) and δ 88.6 (dd, 1J(P-Pt) = 4216.9 Hz, 2J(P-
Figure 3. ORTEP diagram of iodo-triazole 3b top view. The
thermal ellipsoids correspond to 30 % probability
= 7.4 Hz), respectively. The 31P NMR of the BINOL-based
P)
In order to prove that these phosphine-phosphinites can act as
bidentate ligands, we prepared corresponding Pt and Pd
complexes. When 5a was reacted with [PtCl2(COD)] or
complex Pt(8b)Cl2 showed two sets of resonances at δ 88.7 (br,
d, 1J(P-Pt) = 5562 Hz, 2J(PP) = 24 Hz) and at δ 93.7 (d, 1J(P-Pt) = 5542
Hz, 2J(P-P) = 24 Hz).
Pd(MeCN)2Cl2
analytically pure Pt(5a)Cl2 and Pd(5a)Cl2,
respectively, were obtained. In the 31P NMR spectrum the Pt-
complex showed the typical pattern of a complex with a cis-
2.4 Application of triazole based phosphorus ligands in the
Rh-catalyzed hydroformylation
1
coordinated ligand.16 Two doublets at δ -12.4 (br, d, J(P-Pt)
=
3722 Hz, 2J(P-P) = 15 Hz) and at δ 90.6 (d, 1J(P-Pt) = 3864 Hz, 2J(P-P)
= 15 Hz) were observed. Pd(5a)Cl2 was likewise characterized by
two doublets at δ 1.5 (2J(P-P) = 18 Hz) and at δ 120.2 (2J(P-P) = 17
Hz). The analogous complexes Pt(5b,c)Cl2 and Pd(5b,c)Cl2
displayed a similar spectroscopic behavior.
Rhodium-catalyzed hydroformylation of non-branched olefins
is one of the most important processes in industrial homogeneous
catalysis.12 Therefore, the hydroformylation of 1-octene was
chosen to test the activities and regioselectivities induced by the
new phosphorus compounds as ligands in corresponding Rh
catalysts. The required precatalysts were generated in situ by
reaction of [Rh(acac)(COD)] with
5 equivalent of the
2.3 Synthesis of bidentate diphosphite ligands (Type C)
monodentate or 2 equivalent of the bidentate phosphorus ligands.
The reactions were carried out at a temperature of 100 °C under
20 or 50 bar of syngas pressure (CO/H2 ratio 1:1). As solvent
toluene was used. Results are detailed in Table 5. Monodentate
phosphinite and phosphite 2a-h have shown good activity and
moderate till good selectivities compared to classical
monodentate ligands.12,21 In almost all cases rather complete
conversion was noted within 4 h. n-Regioselectivities induced by
diphenylphosphinites 2a-f are moderate and within a narrow
range. Decrease of the syngas pressure from 50 to 20 bars
enhanced the n-regioselectivity without affecting the rate (Table
4, runs 1,3). A further improvement of this parameter up to 75 %
could be achieved by application of the bulky BINOL-derived
phosphites 2g and 2h (Table 4, runs 7,8). Bidentate hybrid
ligands 5a-d also induced only moderate regioselectivity (Runs
9-12). The best value gives the catalyst derived from 5c bearing
electron-withdrawing P-Ar units (Run 12). In comparison to the
literature,12,22 bidentate dipphosphite ligands 8a-c exhibited good
n-selectivities (up to 87 %) and good activity. Interestingly
among the quasi-symmetric ligands 8a-c tested the
diphenylphosphine based ligand 8a induced the highest n-
regioselectivity (Run 13), whereas incorporation of four electron-
withdrawing CF3-groups in the phenyl rings (8c) caused a drastic
Our pathway for the synthesis of quasi-symmetric diphosphite
ligands of type C is shown in Table 4. It is based on the
cyclization of 2-butyne-1,4-diol. Unfortunately, under the smooth
reaction conditions described above only 5 % of the desired diol
was formed. More successful revealed the synthesis via a slightly
modified route recommended by Tikhonova17 and Liu,18 which
proceeds by heating of benzyl bromide with a mixture of but-2-
yne-1,4-diol and sodium azide in DMF at 130 °C for 13 h. 1-
Benzyl-4,5-di(hydroxymethyl)-1H-[1,2,3]triazole (7) which was
only scarcely characterized in the literature was obtained in a
yield of 55 %. Subsequent lithiation of 1,4-diol 7 with two
equivalents of n-BuLi, followed by phosphorylation with ClPAr2
provided diphosphinites 8a,c (Table 4). Likewise the
esterification with (R)-binaphthophosphochloridite proceeded
successfully and gave the diphosphite 8b in nearly quantitative
yield.

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5
lowering of this value (Run 15). The diphosphite 8b forms also a
Solvents were dried and freshly distilled under argon before
very active, but only moderately regioselective catalyst (Run 14).
Table 5. Rhodium-catalyzed hydroformylation of 1-octenea
use. Thin-layer chromatography was performed on pre-coated
TLC plates (silica gel 60 F254, Merck). Flash chromatography
was carried out with silica gel 60 (230–400 mesh ASTM). PCl3
and NEt3 were distilled immediately before use. NMR 1H (250.1,
300.1 and 500.1 MHz), 31P (121.5 MHz), 13C (62.9, 75.5 and
125.7 MHz) and 19F (282 MHz) spectra were recorded on a
Bruker AC 250, ARX 300 and AVANCE 500 respectively.
Chemical shifts δ are quoted in parts per million (ppm) and are
referred to the resonance of tetramethylsilane. 31P NMR chemical
shifts were referenced externally to 85% H3PO4 (δ 0.0). Coupling
constants J are given in Hz. EI mass spectra were measured on a
Finnigan MAT 95-XP mass spectrometer (Thermo Electron
Corporation). HRMS was performed on MAT 95-XP (EI) and
Agilent 6210 Time-of-Flight LC/MS (ESI). GC-MS was
performed on Agilent 5973 chromatograph mass selective
detector. GC was performed on Agilent 7890 A chromatograph
with a 30 m HP5 column.
Run
1
Ligand
2a
p [bar]
20
Conversionb
96
n-Regioselectivityc
67
2b
50
20
50
50
50
20
50
20
50
50
50
50
50
50
50
94
96
98
99
98
94
99
99
94
94
88
94
74
97
95
58
66
59
56
58
75
71
73
68
62
76
54
87
61
53
2
2c
3
2d
4
2e
5
2f
6
2g
7
4.2. Hydroformylations
2h
8
Hydroformylation experiments were carried out in 25 mL or
200 mL autoclaves at 100-120 °C and 20 or 50 bar syngas
(99.997%; CO/H2 = 1:1) for 4 h. The autoclave was purged and
filled with syngas before the precatalyst solution and olefin was
introduced into the reactor. After 4 h the autoclave was cooled to
room temperature and then the pressure was released in a well-
ventilated hood. The reactions mixture was analyzed by gas
chromatography on a HP 5890 Series II or Agilent 7890 A with a
30 m HP5 column to determine conversion and regioselectivity.
2h
9
5ad
5bd
5cd
5dd
8ad
8bd
8cd
10
11
12
13
14
15
16
4.3. X-ray Crystallographic Study of 1f and 3b
a Conditions: [Rh(acac)(cod)], Rh:L:olefin = 1:5:2000, 100 ppm [Rh],
toluene, 4 h; b Determined by GC, cratio of n-nonanal relative to the
overall yield of aldehydes; dRh:L = 1:2.
Data were collected on a Bruker Kappa Apex II diffractometer
using graphite monochromated Mo Kα radiation (λ = 0.71073).
The structures were solved by direct methods (SHELXS-97)19 and
refined by full-matrix least-squares procedures (SHELXL-97).
CCDC-882434 (for 1f) and CCDC-884751 (for 3b) contain the
supplementary crystallographic data for this paper. These data
can be obtained free of charge from The Cambridge
3. Summary and Conclusion
Crystallographic
www.ccdc.cam.ac.uk/data_request/cif.
Data
Centre
via
Three sets of new closely related mono- und bidentate
ligands based on 1,2,3-triazole backbone have been prepared
using click-chemistry approach within two steps. The new
electron deficient P-ligands bearing at least one P-O bond were
prepared from easily available starting materials. Preparation and
isolation of dangerous explosive organic azides could be avoided
in this way. Moreover, a new methodology for the one-pot
synthesis of bidentate ligands via direct dilithiation and
subsequent phosphorylation was developed. In order to prove the
complexation behavior of new ligands corresponding Pt and Pd
complexes were synthesized and characterized. The usefulness of
this type of ligands was demonstrated in the Rh-catalyzed
hydroformylation of 1-octene. In most cases high conversions
and good n-regioselectivities of up to 87 % were achieved.
4.3.1. Crystal data for 1-cyclohexyl-4-
(hydroxymethyl)-1H-1,2,3-triazole (1f):
C9H15N3O, Mr = 181.24, monoclinic, space group P21/c, a =
14.2822(4), b = 8.3517(2), c = 8.0670(3) Å, = 90.00,
94.301(2),
α
β =
γ
= 90.00°, V = 959.53(5) Å3, Z = 4, ρcalcd. = 1.255 g
cm–3, ꢀ = 0.085 mm–1, T = 173(2) K, 2795 independent
reflections, of which 1905 were observed [I>2σ(I)], 122
parameters, final R values [I>2σ(I)]: R1 = 0.0428, wR2 = 0.1002,
final R values (all data): R1 = 0.0758, wR2 = 0.1094, largest diff.
peak and hole 0.28/-0.19 e·Å–3.
4.3.2. Crystal data for 1-(4-methoxybenzyl)-4-
(hydroxymethyl)-5-iodo-1H-1,2,3-triazole (3b)
C11H12IN3O, Mr = 329.14, orthorhombic, space group P212121,
a = 5.8628(1), b = 7.5482(1), c = 26.7283(6) Å, V = 1182.82(4)
Å3, Z = 4, ρcalcd = 1.848 g cm-3, ꢀ = 2.69 mm-1, T = 150(2) K,
2968 independent reflections, of which 2948 were observed [I >
2σ(I)], 147 parameters, final R values [I > 2σ(I)]: R1 = 0.0214,
4. Experimental section
4.1. General methods
Unless otherwise stated, all reactions were carried out under a dry
argon atmosphere using standard Schlenk-line techniques. All
reagents, unless otherwise mentioned, were purchased from
commercial sources and used without additional purification.
wR2 = 0.0528, final
R
values (all data): R1 = 0.0217,
wR2 = 0.0529, largest diff. peak and hole 0.62 and -0.76 e Å-3.

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6
Tetrahedron
[M+H]+. Anal. Calcd. for C10H10FN3O (207.20): C, 57.97; H,
4.4. Synthesis of 1,2,3-triazole 1a-f. General procedure.
4.86; N, 20.28. Found: C, 58.23; H, 4.90; N, 19.77.
A mixture of 1-propinol (2.90 g, 0.05 mol), aryl- or
alkylbromide (0.05 mol), L-proline (1.15 g, 0.01 mmol), sodium
azide (3.90 g, 0.06 mol), sodium carbonate (1.05 g, 0.01 mol) and
sodium ascorbate (2.00 g, 0.01 mol) was stirred in 90 ml DMSO
and H2O 10 ml. CuSO4*5H2O (2.90 g, 0.005 mol) was added
(attention, self-warming). Then the reaction was run at 65 °C for
18 h. The mixture was poured into ice and the product was
extracted with CH2Cl2 (4x150 mL). The combined organic
phases were washed with 5 % ammonia solution (2x150 mL) to
remove traces of azide. The organic layer was washed with brine
(150 mL) and dried over Na2SO4. The organic solvent was
removed under reduced pressure to give the crystalline product.
Additional purification could be achieved via crystallization from
ethyl acetate.
4.4.6. 1-Cyclohexyl-4-(hydroxymethyl)-1H-1,2,3-
triazole (1f)
Colorless crystals, yield 82 % mp 93.5-84.5 °C. 1H NMR (300
MHz, CDCl3): δ = 1.19-1.33 (m, 1H, CH2), 1.37-1.52 (m, 2H,
CH2), 1.66-1.78 (m, 3H, CH2CH2), 1.88-1.94 (m, 2H, CH2), 2.16-
2.21 (m, 2H, CH2), 3.34 (brs, 1H, OH), 4.36-4.47 (m, 1H, CH),
4.76 (s, 2H, CH2), 7.54 (s, 1H, Htrz) ppm. 13C NMR (63 MHz,
CDCl3): δ = 25.1, 33.5 (CH2), 56.3 (CH2OH), 60.1 (CH), 119.4
(CHtrz), 147.2 (Ctrz) ppm. MS (EI, 70 eV): m/z (%) = 181 (21)
[M]+, 83 (29), 82 (19), 55 (100), 41 (49), 39 (28). HRMS (ESI)
for C9H16N3O found: 182.12879 [M+H]+, calcd. 182.12873
[M+H]+. Calcd. for C9H15N3O (181.23): C, 59.64; H, 8.34; N,
23.19. Found: C, 60.08; H, 8.21; N, 22.89.
4.4.1. 1-Benzyl-4-(hydroxymethyl)-1H-1,2,3-
triazole (1a)
4.5. Synthesis of monodentate ligands 2a-f. General
procedure
Colorless crystals, yield 73 %, mp 77-78 °C. For NMR spectra
see Ref.20
A solution of 1.6 M n-BuLi (0.94 ml, 0.0015 mol) was added
to a solution of the triazole (0.0015 mol) in THF (20 mL) at -78
°C. The resulting mixture was allowed to warm up to ambient
temperature and stirred for 30 min. Afterwards, the reaction
4.4.2. 1-(4-Methylbenzyl)-4-(hydroxymethyl)-1H-
1,2,3-triazole (1b)
mixture
was
added
slowly
to
a
solution
of
Colorless crystals, yield 93 %, mp 91.5-92.5 °C. For NMR
spectra see Ref.20
diphenylchlorophosphine (0.33 g, 0.0015 mol) in 5 ml THF at 0
°C. The mixture was warmed to ambient temperature and stirred
overnight. Then the solvent was evaporated under reduced
pressure. The residue was transferred into toluene (10 mL), and
the solution was filtered to give the pure product in nearly
quantitative yield.
4.4.3. 1-(4-Fluorobenzyl)-4-(hydroxymethyl)-1H-
1,2,3-triazole (1c)
Colorless crystals, yield 88 % mp 67-68 °C. For NMR spectra
see Ref.20
4.5.1. 1-Benzyl-4-(diphenylphosphinoxymethyl)-1H-
1,2,3-triazole (2a)
4.4.4. 1-(4-Trifluoromethylbenzyl)-4-
(hydroxymethyl)-1H-1,2,3-triazole (1d)
Colorless powder, yield 0.547 g (97.7 %). 1H NMR (300
3
1
MHz, CDCl3): δ = 4.93 (d, 2H, J(H-P) = 10.4 Hz, CH2O), 5.38 (s,
Colorless crystals, yield 94 % mp 99.5-100.5 °C. H NMR
2H, CH2), 7.10-7.14 (m, 2H, CHAr), 7.20-7.29 (m, 10 H, CHAr
(300 MHz, CDCl3): δ = 3.47 (br, 1H, OH), 4.75 (s, 2H, CH2OH),
3
and Htrz), 7.32-7.40 (m, 4H, CHAr) ppm. 13C NMR (75.5 MHz,
5.56 (s, 2H, CH2), 7.35 (d, J(H-H) = 8.12 Hz, 2H, CHAr), 7.5 (s,
2
1H, Htrz) 7.61 (d, 3J(H-H) = 7.93 Hz, 2H, CHAr) ppm. 13C NMR (63
MHz, CDCl3): δ = 53.5 (CH2), 56.3 (CH2OH), 121.8 (CHtrz),
CDCl3): δ = 54.1 (CH2), 63.5 (d, J(C-P) = 21 Hz, CH2O), 122.4
(C5trz), 128.0 (CAr), 128.3 (Cm-P, d, J(C-P) = 6.8 Hz, CAr), 128.7
(Cp-P), 129.1 (CAr), 129.5 (CAr), 130.6 (Co-P, d, J(C-P) = 22 Hz,
3
2
1
3
123.7 (q, J(C-F) = 272.4 Hz, CF3), 126.1 (q, J(C-F) = 3.6 Hz,
1
2
CAr), 134.5 (q, CAr), 141.2 (q, CP, d, J(C-P) = 18 Hz, CAr), 146.2
CHAr), 128.2 (CHAr), 131.1 (q, J = 32.5 Hz, CCF3), 138.4 (CAr),
(q, C4trz, d, 3J(C-P) = 8 Hz). 31P NMR (121.5 MHz, CDCl3): δ 116.0
ppm. MS (EI, 70 eV): m/z (%) = 373 (38) [M]+, 372 (35) [M-1]+,
249 (82), 201 (100) [Ph2PO]+, 91 (58). HRMS (ESI) for
C22H21N3OP found: 374.1422 [M+H]+, calcd. 374.1417 [M+H]+.
HRMS (ESI) for C22H20N3NaOP found: 396.1242 [M+Na]+;
calcd. 396.1236 [M+Na] +.
148.4 (Ctrz) ppm. 19F NMR (282 MHz, CDCl3): δ = -62.8 ppm.
MS (EI, 70 eV): m/z (%) = 257 (2) [M]+, 159 (100), 109 (28).
HRMS (ESI) for C11H11F3N3O found: 258.08487 [M+H]+, calcd.
258.08511 [M+H]+. Calcd for C11H10F3N3O (257.21): C, 51.37;
H, 3.92; N, 16.34. Found: C, 51.70; H, 3.88; N, 16.29.
4.4.5. 1-(3-Fluorobenzyl)-4-(hydroxymethyl)-1H-
1,2,3-triazole (1e)
4.5.2. 1-(4-Methylbenzyl)-4-
(diphenylphosphinoxymethyl)-1H-1,2,3-triazole (2b)
Colorless crystals, yield 82 % mp 70.5-71.5 °C . 1H NMR (300
MHz, CDCl3): δ = 3.24 (brs, 1H, OH), 4.69 (s, 2H, CH2OH), 5.43
(s, 2H, CH2), 6.85-6.90 (m, 1H, CHAr), 6.93-7.00 (m, 2H, CHAr ),
7.23-7.30 (m, 1H, CHAr ), 7.42 (s, 1H, Htrz) ppm. 13C NMR (75
Colorless powder, yield 0.571 g (98.3 %). 1H NMR (300
3
MHz, CDCl3): δ = 2.27 (3H, s, CH3), 4.91 (2H, d, J(H-P) = 10.3
Hz, CH2O), 5.33 (2H, s, CH2), 6.99-7.10 (m, 4H, CHAr), 7.20-
7.26 (m, 7 H, CHAr and Htrz), 7.32-7.40 (m, 4H, CHAr) ppm. 13C
NMR (62.9 MHz, CDCl3): δ = 21.2 (CH3), 53.8 (CH2), 63.4 (d,
2J(C-P) = 21 Hz, CH2O), 122.3 (C5trz), 128.1 (CAr), 128.3 (Cm-P, d,
3J(C-P) = 7 Hz, CAr), 129.4 (Cp-P), 129.7 (CAr), 130.5 (Co-P, d, 2J(C-P)
= 22 Hz, CAr), 131.5 (q, CAr), 138.6 (q, CCH3), 141.2 (q, CP, d,
2
Hz, CDCl3): δ = 53.4 (CH2), 56.2 (CH2OH), 115.0 (d, J = 22.0
Hz, CHAr), 115.7 (d, 2J = 20.9 Hz, CHAr), 121.8 (CHtrz), 123.5 (d,
3
3
4J = 3.3 Hz, CHAr), 130.7 (d, J = 8.3 Hz, CHAr), 136.8 (d, J =
1
7.7 Hz, CAr), 148.3 (Ctrz), 162.9 (d, J = 247.6 Hz, CF) ppm. 19F
NMR (282 MHz, CDCl3): δ = -111.6 ppm. MS (EI, 70 eV): m/z
(%) = 207 (2) [M]+, 161 (12), 109 (100), 83 (19). HRMS (ESI)
for C10H11FN3O found: 208.08807 [M+H]+, calcd. 208.08842
1J(C,P) = 18 Hz, CAr), 146.1 (q, C4trz, d, J = 8 Hz) ppm. 31P NMR
3
(121.5 Hz, CDCl3): δ = 115.9 ppm. MS (EI, 70 eV): m/z (%) =
387 (9) [M]+, 386 (4) [M-H]+, 263 (63), 202 (44), 201 (96), 105

ACCEPTED MANUSCRIPT
7
(100). HRMS (ESI) for C23H23N3OP found: 388.15733 [M+H]+,
calcd. 388.15719 [M+H]+. HRMS (ESI) for C23H22N3NaOP
found: 426.13418 [M+Na]+, calcd. 426.1341 [M+Na]+.
(m, 2H, CH2), 4.25-4.36 (m, 1H, CH), 4.95 (dd, J = 0.6 Hz ,
3JP-H = 10.4 Hz, 2H, CH2), 7.25 – 7.29 (m, 6H, CHAr), 7.31 (s,
1H, Htrz), 7.38-7.43 (m, 4H, CHAr) ppm. 13C NMR (75 MHz,
2
CDCl3): δ = 25.1, 33.4 (CH2) 59.9 (CH), 63.6 (d, J = 20.9 Hz,
4.5.3. 1-(4-Fluorobenzyl)-4-
3
CH2), 120.1 (CHtrz), 128.3 (d, J = 6.6 Hz, CHAr), 129.4 (CHAr),
(diphenylphosphinoxymethyl)-1H-1,2,3-triazole (2c)
130.5 (d, 2J = 21.5 Hz, CHAr), 141.3 (d, 1J = 17.6 Hz, CAr), 145.2
Colorless powder, yield 0.580 g (99 %). 1H NMR (300 MHz,
(d, J = 8.3 Hz, Ctrz) ppm. 31P NMR (121 MHz, CDCl3): δ =
3
3
CDCl3): δ = 4.93 (2H, d, J(H-P) = 10.5 Hz, CH2O), 5.35 (2H, s,
115.7 ppm. HRMS (ESI) for C21H25N3OP found: 366.17313
[M+H]+, calcd. 366.17298 [M+H]+.
CH2), 6.92-7.00 (m, 2 H, CHAr), 7.07-7.14 (m, 2 H, CHAr), 7.21–
7.28 (m, 7 H, CHAr and Htrz), 7.32-7.41 (m, 4 H, CHAr) ppm. 13C
2
NMR (75.5 MHz, CDCl3): δ 53.3 (CH2), 63.5 (d, J(C-P) = 21 Hz,
2
CH2O), 116.1 (Co-F, d, J(C,F) = 22 Hz), 122.3 (C5trz), 128.3 (Cm-P
,
4.6. Synthesis of monodentate ligands 2g-h. General
procedure
3
3
d, J(C-P) = 7 Hz), 129.5 (Cp-P), 129.9 (Cm-F, d, J(C,F) = 8.2 Hz),
2
130.4 (q, Cp-F), 130.5 (Co-P, d, J(C-P) = 22 Hz), 141.2 (q, CP, d,
1J(C,P) = 18 Hz), 146.3 (q, C4trz, d, J(C,P) = 8 Hz), 162.9 (q, CF, d,
3
1-Methylpyrrolidin-2-one (0.01 g, 0.1 mmol) was added to a
stirred mixture of (R)-binaphthol (0.429 g, 0.0015 mol) and PCl3
(4 mL). The mixture was refluxed for 20 min until it became
completely homogeneous. Subsequently all volatiles were
removed under vacuum. Toluene (5 mL) was added and the
solvent was evaporated on a vacuum line to remove traces of
PCl3. The product binaphtholchlorophosphite was dried under
vacuum for 1 h. In a separate vessel a solution of 1.6 M n-BuLi
(0.94 mL, 0.0015 mol) was added to a solution of the relevant
triazole (0.0015 mol) in THF (20 mL) at -78 °C. The resulting
orange mixture was allowed to warm up to ambient temperature
and stirred for 30 min. This mixture was added slowly to a stirred
solution of binaphtholchlorophosphite in THF (5 mL) at 0 °C.
The reaction mixture was stirred overnight at room temperature.
The solvent was evaporated under reduced pressure. The residue
was transferred into toluene (10 mL) and the solution was filtered
off to give the pure product as a lightly yellow foam.
1J(C,F) = 248 Hz) ppm. 31P NMR (121.5 Hz, CDCl3): δ = 115.9
ppm. 19F NMR (282 MHz, CDCl3): δ = -112.3 ppm. HRMS (ESI)
for C22H20FN3OP found: 392.13313 [M+H]+, calcd. 392.132225
[M+H]+. HRMS (ESI) for C22H19FN3NaOP found 414.1153
[M+Na]+, calcd. 414.1142 [M+Na]+.
4.5.4. 1-(4-Trifluoromethylbenzyl)-4-
(diphenylphosphinoxymethyl)-1H-1,2,3-triazole (2d)
Colorless powder, yield 0.658 g (99.5 %). 1H NMR (300
3
MHz, CDCl3): δ = 4.96 (dd, J = 0.6 Hz, J(P-H) = 10.6 Hz, 2H,
CH2OP), 5.45 (s, 2H, CH2), 7.19 (m, 1H, CHAr), 7.22-7.25 (m,
7H, CHAr), 7.28 (s, 1H, Htrz), 7.34-7.40 (m, 4H, CHAr) 7.51-7.54
(m, 2H, CHAr) ppm. 13C NMR (75 Hz, CDCl3): δ = 53.2 (CH2),
3
1
63.3 (d, J(C-P) = 20.9 Hz, CH2OP), 122.5 (CHtrz), 123.8 (q, J(C-F)
3
= 272.3 Hz, CF3), 125.9 (q, J(C-F) = 3.9 Hz, CHAr), 128.0 (CHAr),
128.2 (d, J(C-P) = 7.2 Hz, CHAr) 129.4 (CHAr), 130.4 (d, J(C-P)
22.0 Hz, CHAr) 130.7 (q, J(C-F) = 32.5 Hz, CCF3), 138.5 (CAr),
3
2
=
2
1
3
4.6.1. 4-Dinaphtho[1,2-f:2´,1´-
d][1,3,2,]dioxaphosphephin-4-yloxymethyl-1-(4-
fluorobenzyl)- 1H-1,2,3-triazole (2g)
141.1 (d, J(C-P) = 18.2 Hz, CAr), 146.4 (d, J(C-P) = 7.7 Hz, Ctrz)
ppm. 31P NMR (121 MHz, CDCl3): δ = 116.2 ppm. 19F NMR
(282 MHz, CDCl3):
δ = -62.8 ppm. HRMS (ESI) for
C23H20F3N3OP found: 442.12818 [M+H]+, calcd. 442.12906
Colorless solid. Yield 0.752 g (96.3 %). 1H NMR (300 MHz,
[M+H]+
3
C6D6): δ = 4.76 (2H, d, J(H-P) = 1.2 Hz, CH2O), 5.00-5.19 (2H,
.
m, CH2), 6.67-7.75 (m, 17 H, CHAr and Htrz), ppm. 13C NMR
(75.5 MHz, C6D6): δ 52.7 (CH2), 58.8 (d, 2J(C,P) = 4.5 Hz, CH2O),
2
4.5.5. 1-(3-Fluorobenzyl)-4-
115.3 (Co-F, d, J(C,F) = 22 Hz), 121.5 (d, J = 5.8 Hz, CAr), 122.0
(diphenylphosphinoxymethyl)-1H-1,2,3-triazole
(2e):
(C5trz), 124.7 (d, J = 12 Hz, CAr), 126.2 (d, J = 3.2 Hz, CAr), 126.7
(d, J = 9.2 Hz, CAr), 128.2 (CAr), 129.4 (d, J = 8.2 Hz Cm-F, d,
2
3J(C,F) = 8.2 Hz), 130.2 (d, Co-P, d, J(C-P) = 22 Hz), 130.8 (q, CAr),
Colorless solid, yield 0.584 g (99.4 %). 1H NMR (300 MHz,
CDCl3): δ = 4.94 (dd, J = 0.6 Hz, 3J(P-H) = 10.6 Hz, 2H, CH2OP),
5.37 (s, 2H, CH2), 6.79-6.84 (m, 1H, CHAr), 6.88-6.91 (m, 1H,
CHAr), 6.93-7.00 (m, 1H, CHAr), 7.23-7.26 (m, 8H, CHAr and
Htrz), 7.35-7.40 (m, 4H, CHAr) ppm. 13C NMR (75 MHz, CDCl3):
131.4 (q, CAr), 132.6 (q, d, J = 22.9 Hz, CAr), 144.9 (q, d, J(CP)
=
=
4.4 Hz, CAr), 148.0 (q, d, J(CP) = 2.2 Hz, CAr), 149.5 (q, d, J(CP)
1
5.3 Hz, CAr), 163.0 (q, CF, d, J(C,F) = 246 Hz) ppm. 31P NMR
(75.5 MHz, C6D6): δ = 151.9 ppm, 19F NMR (282.4 MHz, C6D6):
δ = -113.2 ppm. MS (EI, 70 eV): m/z (%) = 521 (2) [M]+, 286
4
2
δ = 53.4 (d, J(C-F) = 2.2 Hz, CH2), 63.5 (d, J(C-P) = 21.5 Hz,
(53)
[binaphthdioxy]+, 105 (100). HRMS (ESI) for
CH2OP), 115.0 (d, 2J(C-F) = 22.6 Hz, CHAr), 115.8 (d, 2J(C-F) = 20.9
Hz, CHAr), 122.5 (CHtrz), 123,5 (d, JC-F = 2.8 Hz, CHAr), 128.3
C30H22FN3O3P found: 522.13841 [M+H]+, calcd. 522.13773
[M+H]+. HRMS (ESI) for C30H21FN3NaO3P found: 544.12062
[M+Na]+, calcd. 544.11968 [M+Na]+.
4
3
2
(d, J(C-P) = 6.6 Hz, CHAr), 129.5 (CHAr), 130.6 (d, J(C-P) = 21.5
Hz, CHAr), 130.8 (CHAr) 136.9 (d, 3J(C-F) = 7.7 Hz, CAr), 141.2 (d,
JC-P = 17.6 Hz, CAr), 146.4 (d, 3J(C-P) = 7.7 Hz, Ctrz), 163.0 (d, 1J(C-
= 247.6 Hz, CF) ppm. 31P NMR (121 MHz, CDCl3): δ = 116.3
F)
ppm. 19F NMR (282 MHz, CDCl3): δ = -111.6 ppm. HRMS (ESI)
4.6.2. 4-Dinaphtho[1,2-f:2´,1´-
for C22H20FN3OP [M+H]+ found: 392.13272 [M+H]+, calcd.
d][1,3,2,]dioxaphosphephin-4-yloxymethyl-1-(4-
methylbenzyl)-1H-1,2,3-triazole (2h)
392.13225 [M+H]+
.
Colorless solid. Yield 0.728 g (93.4 %). 1H NMR (300 MHz,
3
C6D6): δ = 2.12 (3H, s, CH3), 4.91 (2H, d, J(H-P) = 2.4 Hz,
4.5.6. 1-Cyclohexyl-4-
(diphenylphosphinoxymethyl)-1H-1,2,3-triazole
CH2O), 4.98-5.95 (2H, m, CH2), 6.80-7.78 (m, 17 H, CAr and
Htrz), ppm. 13C NMR (75.7 MHz, C6D6): δ = 21.0 (CH3), 53.4
2
(2f):
(CH2), 58.8 (d, J(C,P) = 4.3 Hz, CH2), 122.5 (d, J = 6.8 Hz, CAr),
Colorless solid, yield 0.544 g (99.3 %). 1H NMR (300 MHz,
CDCl3): δ = 1.14-1.24 (m, 1H, CH2), 1.27-1.47 (m, 2H, CH2),
1.51-1.66 (m, 3H, CH2CH2), 1.78-1.85 (m, 2H, CH2), 2.03-2.09
122.6 (C5trz), 125.3 (d, J = 12 Hz, CAr), 126.6 (d, J = 3.4 Hz, CAr),
127.4 (d, J = 10 Hz, CAr), 128.8 (d, J = 8.9 Hz, CAr), 128.7 (CAr),
129.7 (CAr), 130.8 (d, J = 18 Hz, CAr), 131.5 (q, CAr), 132.5 (q,

ACCEPTED MANUSCRIPT
8
Tetrahedron
CAr), 133.6 (q, d, J = 23.4 Hz, CAr), 138.2 (q, CAr), 144.8 (q, d,
was transferred into toluene (10 mL) and the solution was filtered
to give the pure product in nearly quantitative yield.
J(CP) = 4.4 Hz, CAr), 148.0 (q, d, J(CP) = 2.2 Hz, CAr), 149.5 (q, d,
J(CP) = 5.3 Hz, CAr), 31P NMR (121.5 MHz, C6D6): δ = 152.1 ppm.
MS (EI, 70 eV): m/z (%) = 518 (11) [M + H]+, 517 (34) [M]+,
332 (94) [binaphthdioxy-PO: C20H12O3P], 286 (97)
[binaphthdioxy]+, 105 (100). HRMS (ESI) for C31H25N3O3P
found: 518.16347 [M+H]+, calcd. 518.1628 [M+H]+. HRMS
(ESI) for C31H24FN3NaO3P found: 540.14582 [M+Na]+, calcd.
540.14475 [M+Na]+.
4.8.1.1-Benzyl-4-(diphenylphosphinoxymethyl)-5-
diphenylphosphino- 1H-1,2,3-triazole (5a)
Colorless solid, yield 0.819 g (98 %). 1H NMR (500 MHz,
CDCl3): 4.13 (2H, d, J(H-P) = 7.5 Hz, CH2O), 5.90 (2H, s, CH2),
3
6.95-7.38 (m, 25 H, CHAr) ppm. 13C NMR (125 MHz, CDCl3): δ
= 53.2 (d, J = 10.2 Hz, CH2), 62.2 (d, J = 21.9 Hz, CH2), 127.8
(CAr), 128.1 (d, J = 7.0 Hz, CAr), 128.3 (d, J = 6.7 Hz, CAr), 128.4
(CAr), 128.7 (d, J = 7.0 Hz, CAr), 129.1 (CAr), 129.3 (CAr), 130.6
(d, J = 21.6 Hz, CAr), 133.2 (d, J = 20.2 Hz, CAr), 133.9-134.4 (q,
m, CAr), 134.9 (q, CAr), 141.5 (q, d, J = 18.4 Hz, CAr), 150.6 (q, d,
J = 11.0 Hz, CAr) ppm. 31P NMR (121.5 MHz, C6D6): δ = -20.8,
130.0 ppm. MS (EI, 70 eV): m/z (%) = 557 (5) [M]+, 314 (10)
[M-Ph2PO-N2]+, 201 (52) [Ph2PO]+, 91 (100). HRMS (ESI) for
C34H30N3OP2 found: 558.18587 [M+H]+; calcd. 558.18587
[M+H]+.
4.7. Synthesis of iodides 3a-b. General procedure.
1.6 M n-BuLi in THF (1.88 mL, 0.003 mol) was added to a
solution of the relevant triazole (0.0015 mol) in THF (20 mL) at -
78 °C. The resulting red-orange mixture was stirred for 30 min
at room temperature. Afterwards, the reaction mixture was
cooled to -78 °C and a solution of I2 (0.381 g, 0.0015 mol) in 10
ml THF was added slowly. The mixture was stirred at ambient
temperature overnight and then the reaction was quenched with
aqueous NH4Cl solution (10 ml). The product was extracted with
diethyl ether (3×50 mL). The organic layer was washed with an
aqueous solution of Na2S2O3 (10 mL) and brine (3×100 mL). The
organic phase was dried over Na2SO4 and evaporated under
reduced pressure. The residue was crystallized from ethyl acetate
to give the product as light yellow crystals.
4.8.2.
1-(4-Methylbenzyl)-4-(diphenylphosphinoxymethyl)-5-
diphenylphosphino-1H-1,2,3-triazole (5b)
1
Colorless solid, yield 0.840 g (98 %). H NMR (300 MHz,
C6D6): δ = 2.04 (3H, s, CH3), 4.55 (2H, d, J(H-P) = 7.6 Hz,
3
CH2O), 5.49 (2H, s, CH2), 6.76 (2H, d, J = 7.9 Hz, CHAr), 6.92-
7.71 (m, 22 H, CHAr), ppm. 13C NMR (75.5 MHz, C6D6): δ =
20.9 (CH3), 52.9 (d, J = 10.2 Hz, CH2), 62.8 (d, J = 21.9 Hz,
CH2), 128.2 (d, J = 1.5 Hz, CAr), 128.5 (d, J = 6.8 Hz, CAr), 128.9
(d, J = 7.6 Hz, CAr), 129.2-129.3 (m, CAr), 131.1 (d, J = 21.8 Hz,
CAr), 132.8 (q, CAr), 133.5 (d, J = 20.6 Hz, CAr), 134.4-135.0 (q,
m, CAr), 137.5 (q, CAr), 142.5 (q, d, J = 19.5 Hz, CAr), 151.0 (q,
d, J = 11.2 Hz, CAr) ppm. 31P NMR (121.5 MHz, C6D6): δ = -
20.7, 129.9 ppm. MS (EI, 70 eV): m/z (%) = 571 (6) [M]+, 370
(23) [M-Ph2PO]+, 201 (72) [Ph2PO]+, 183 (100), 105 (71).
HRMS (ESI) for C35H32N3OP2 found: 572.2022 [M+H]+; calcd.
572.2015 [M+H]+. HRMS (ESI) for C35H31N3NaOP2 found:
594.18434 [M+Na]+, calcd. 594.18346 [M+Na]+.
4.7.1. 1-Benzyl-4-(hydroxymethyl)-5-iodo-1H-1,2,3-triazole (3a)
Light yellow crystals. Yield: 0.393 g (83.1 %) mp (decomp.)
1
120 °C. H NMR (300 MHz, CDCl3): δ = 3.35 (1H, br. s, OH),
4.60 (2H, s, CH2), 5.47 (2H, s, CH2), 7.14-7.28 (5H, m, CAr) ppm.
13C NMR (75.5 MHz, CDCl3): δ = 54.3 (CH2), 56.5 (CH2), 78.8
(q, C5trz), 127.9 (CAr), 128.6 (CAr), 129.0 (CAr), 134.1 (q, CAr),
151.2 (q, CAr) ppm. MS (EI, 70 eV): m/z (%) = 315 (0.5) [M]+,
188 (78) [M–I]+, 91 (100). HRMS (ESI) for C10H11IN3O
315.9946 found: [M+H]+, calcd. 315.9941 [M+H]+. HRMS (ESI)
for C10H10IN3NaO found: 337.9766 [M+Na]+, calcd. 337.9761
[M+Na]+.
4.7.2.
1-(4-Methylbenzyl)-4-(hydroxymethyl)-5-iodo-1H-1,2,3-
4.8.3.
1-(4-Methylbenzyl)-4-[bis[3,5-bis(trifluoromethyl)
triazole (3b)
phenyl]-phosphinoxymethyl)-5-[bis(3,5-bis(trifluoromethyl)
phenyl)-phosphino]-1H-1,2,3-triazole (5c)
Light yellow crystals. Yield: 0.420 g (82.5 %) mp (decomp.)
152 °C. 1H NMR (300 MHz, CDCl3): δ = 2.24 (3H, s, CH3), 3.05
(1H, br. S, OH), 4.62 (2H, s, CH2), 5.45 (2H, s, CH2), 7.07 (2H,
s, CAr), 7.09 (2H, s, CAr), ppm. 13C NMR (75.5 MHz, CDCl3): δ =
21.2 (CH3), 54.1 (CH2), 56.5 (CH2), 78.8 (q, C5trz), 127.9 (CAr),
129.5 (CAr), 131.1 (q, CAr), 138.4 (q, CAr), 151.2 (q, CAr) ppm.
HRMS (ESI) for C11H13IN3O found: 330.00962 [M+H]+, calcd.
330.00978 [M+H]+. HRMS (ESI) for C11H12IN3NaO found:
351.99182 [M+Na]+; calcd. 351.99173 [M+Na]+.
1
Colorless solid, yield 1.589 g (95 %). H NMR (300 MHz,
CDCl3): δ = 2.00 (3H, s, CH3), 4.30 (2H, d, J(H-P) = 11.9 Hz,
3
CH2O), 5.75 (2H, s, CH2), 6.70 (2H, d, J = 7.7 Hz, CHAr), 6.83
(2H, d, J = 8.1 Hz, CHAr), 7.34-7.82 (m, 12 H, CHAr) ppm. 13C
NMR (125 MHz, CDCl3): δ = 20.9 (CH3), 52.8 (d, J = 10.1 Hz,
CH2), 63.2 (d, J = 22.4 Hz, CH2), 120.4 (d, J = 23.9 Hz, CAr),
124.2-124.9 (br, m, CAr), 126.4-126.8 (br, m, CAr), 127.4 (CAr),
128.7 (CAr), 129.1 (CAr), 129.0 (d, J = 17.1 Hz, CAr), 129.5-130.3
(br, m, CAr), 130.6-131.6 (m, CAr), 131.6-133.5 (m, CAr), 137.4
(d, J = 17.9 Hz, CAr), 143.1 (CAr), 142.3 (d, J = 20 Hz, CAr), 143.1
(CAr), 143.5 (CAr), 144.6 (CAr) ppm. 31P NMR (121.5 MHz,
CDCl3): δ = -35.9, 114.6 ppm. 19F NMR (282 MHz, CDCl3): δ =
- 63.2, -63.4 ppm. MS (EI, 70 eV): m/z (%) = 1115 (3) [M]+, 614
(13) [M – Ar2PO-N2]+, 473 (41) [Ar2PO]+, 457 (25) [Ar2P]+, 105
(100). HRMS (ESI) for C43H24F24N3NOP2 found: 1116.1009
[M+H]+, calcd. 1116.1006 [M+H]+.
4.8. Synthesis of bidentate hybrid ligands 5a-f. General
procedure
1.6 M n-BuLi in THF (1.88 ml, 0.003 mol) was added to a
solution of the relevant triazole (0.0015 mol) in THF (20 mL) at -
78 °C. The resulting red mixture was stirred for 30 min at
ambient temperature. Afterwards, the reaction mixture was
cooled to -78 °C and a solution of diphenylchlorophosphine
(0.66 g, 0.003 mol) in THF (10 ml) slowly added at -78 °C. The
mixture was stirred overnight at ambient temperature. The
solvent was then evaporated under reduced pressure. The residue
4.8.4.
1-(4-Fluorobenzyl)-4-(diphenylphosphinoxymethyl)-5-
diphenylphosphino-1H-1,2,3-triazole (5d)

ACCEPTED MANUSCRIPT
9
1
1
Colorless solid, yield 0.837 g (97 %). H NMR (300 MHz,
Colorless solid, yield 1.233 g (97 %). H NMR (300 MHz,
3
C6D6): δ = 4.55 (2H, d, J(H-P) = 7.9 Hz, CH2O), 5.35 (2H, s,
C6D6): δ = 4.54-4.81 (2H, m, CH2), 4.89-5.12 (2H, m, CH2), 5.15
3
CH2), 6.78-6.74 (2H, m, CHAr), 6.94-7.70 (m, 22 H, CHAr) ppm.
(2H, d, J(H-P) = 14.7 Hz), 6.95-7.78 (m, 29 H, Ar), ppm. 13C
13C NMR (121.5 MHz, C6D6): δ = 52.2 (d, J = 10 Hz, CH2), 62.7
NMR (75.5 MHz, C6D6): δ = 50.7 (CH2O), 52.1 (CH2O), 56.5 (d,
2J(C,P) = 2.8 Hz, CH2O), 121.3-122.4 (m, CAr), 125.1-125.7 (m,
CAr), 126.6 (d, J = 2.6 Hz, CAr), 126.9 (d, J = 3.5 Hz, CAr), 127.3
(t, J = 9.1 Hz, CAr), 127.8 (CAr), 128.3 (CAr), 128.6 (d, J = 14 Hz,
CAr), 128.8 (d, J = 14 Hz, CAr), 129.3 (CAr), 130.7 -131.2 (m,
CAr), 133.7 (q, CAr), 136.5 (q, CAr), 141.8 (q, d, J = 4.4 Hz, CAr),
146.2 (q, d, J = 2.4 Hz, CAr), 146.7 (q, d, J = 2.2 Hz, CAr), 147.5
(q, d, J = 5.3 Hz, CAr), 148.2 (q, d, J = 5.3 Hz, CAr), 31P NMR
(121.5 MHz, C6D6): δ = 149.8, 150.7 ppm. MS (EI, 70 eV): m/z
(%) = 583 (11), 332 (85), 286 (100) [binaphthdioxy]+. HRMS
(ESI) for C51H36N3O6P2 found: 848.20786 [M+H]+, calcd.
848.20739 [M+H]+. HRMS (ESI) for C51H35N3NaO6P2 found:
870.19055 [M+Na]+, calcd. 870.18933 [M+Na]+.
2
(d, J = 22 Hz, CH2), 115.3 (Co-F, d, J(C,F) = 21.8 Hz), 128.4 (d, J
= 6.8 Hz, CAr), 128.9 (d, J = 7.6 Hz, CAr), 129.4 (d, J = 6.8 Hz,
CAr), 129.3 (q, Cp-P), 129.4 (q, Cp-P), 130.4 (q, Cp-F), 131.0 (d, J =
21.8 Hz, CAr), 133.5 (d, J = 20 Hz, CAr), 135.6-136.1 (q, m, CAr),
142.4 (q, CP, d, 1J(C,P) = 19 Hz, CAr), 151.1 (q, d, J = 11 Hz, CAr),
162.5 (q, CF, d, J(C,F) = 246 Hz) ppm. 31P NMR (121.5 MHz,
1
C6D6): δ -= 35.3, 114.9 ppm. 19F NMR (282 MHz, C6D6): δ = -
115.0 ppm. MS (EI, 70 eV): m/z (%) = 576 (6) [M+1]+, 575 (15)
[M]+, 498 (16), 482 (16), 362 (47) [M-Ph2P-N2]+, 201 (95)
[Ph2PO]+, 109 (100). HRMS (ESI) for C34H29FN3OP2 found:
576.17600 [M+H]+, calcd. 576.17644 [M+H]+. HRMS (ESI) for
C34H28FN3NaOP2 found: 598.15755 [M+Na]+, 598.15838 (calcd.)
[M+Na]+.
4.10.3.
1-Benzyl-4,5-bis[3,5-bis(trifluoromethyl)phenyl]-1H-
4.9. 1-Benzyl-4,5-di(hydroxymethyl)-1H-[1,2,3]triazole (7)
1,2,3-triazole (8c)
1
The synthesis was carried out according to the slightly
modified procedure of Liu.[18] Benzyl bromide (22.23 g, 15.44
mL, 0.13mol) was added to the suspension of but-2-yne-1,4-diol
(8.6g, 0.1mol) and sodium azide (7.8g, 0.12mol) in 50mL DMF
at room temperature (attention, self-warming). The mixture was
stirred at 130 °C for 18 h. Colorless crystals, yield 53 %, mp
104.5-105.5. 1H NMR (300.1 MHz, CDCl3): δ = 4.45 (2H, s,
OCH2), 4.53 (2H, s, OCH2), 4.72-5.21 (2H, br. s, OH), 5.45 (2H,
s, CH2Ph), 7.08-7.25 (5H, m, CHAr), 13C NMR (75.5 MHz,
CDCl3): δ = 52.0 (CH2O), 52.3 (CH2O), 55.1 (CH2Ph), 127.6
(CAr), 128.3 (CAr), 128.9 (CAr), 134.3 (q, CAr), 134.7 (q, CAr),
145.1 ( q, CAr).
Colorless solid, yield 1.629 g (96 %). H NMR (300 MHz,
C6D6): δ = 4.35 (2H, d, J = 10.9 Hz, CH2O), 4.92 (2H, d, J = 11.9
Hz, CH2O), 5.04 (2H, s, CH2), 6.79-7.68 (m, 9 H, CHAr), 7.71
(4H, d, J = 6.8 Hz, CHAr), 7.93 (4H, d, J = 6.4 Hz, CHAr) ppm.
13C NMR (75.5 MHz, C6D6): δ = 52.4 (CH2), 58.9 (d, J(C,P) = 24
2
Hz, CH2), 63.5 (d, 2J(C,P) = 24 Hz, CH2), 121.5 (q, d, J = 17.1 Hz,
CAr), 123.8-124.7 (br, m, 4 C, CAr), 125.1 (d, J = 17.4 Hz, CAr),
127.1 (CAr), 128.3 (CAr), 128.7 (CAr), 129.1 (CAr), 129.5-130.3
(br, m, 8C, CAr), 130.9 (q, d, J = 7 Hz, CAr), 131.6-133.5 (m, CAr),
134.3 (q, CAr), 138.0 (q, d, J = 19.0 Hz, CAr), 142.9 (q, d, J =
24.3 Hz, CAr), 143.6 (q, d, J = 6.1 Hz, CAr), 144.2 (q, d, J = 24.7
Hz, CAr) ppm. 31P NMR (121.5 MHz, C6D6): δ = 122.3, 122.8
ppm, 19F NMR (282 MHz, CDCl3): δ = -63.0, -63.1 ppm. HRMS
(ESI) for C43H24F24N3O2P2
found: 1132.09668 [M+H]+,
1132.0955 calcd. [M+H]+.
4.10. Synthesis of bidentate ligands 8a-c. General procedure
The synthesis of bidentate ligand 8a-c was performed analog
to the synthesis of ligands 5a-d. Yields were nearly quantitative.
4.11. Synthesis of Pt(5a-b)Cl2 and Pt(8a) complex. General
procedure
To a stirred suspension of Pt(COD)Cl2 (0.187 g, 0.0005 mol)
in CH2Cl2 (8 mL) a solution of ligand 5a or 5b (0.0005 mol) in
CH2Cl2 (8 mL) was added dropwise and the reaction mixture was
stirred overnight at ambient temperature. Then the solvent was
evaporated and the obtained solid was dried in vacuum. Yields
were nearly quantitative.
4.10.1. 1-Benzyl-4,5-bis(diphenylphosphinoxymethyl)-1H-1,2,3-
triazole (8a)
1
Colorless solid, yield 0.873 g (99 %). H NMR (300 MHz,
3
3
C6D6): δ = 4.66 (2H, d, J(H-P) = 9.0 Hz), 5.15 (2H, d, J(H-P)
=
10.0 Hz), 5.20 (2H, s, CH2), 6.95-7.20 (m, 17 H, Ar), 7.44-7.52
(4H, m, Ar), 7.63-7.71 (4H, m, Ar) ppm. 13C NMR (75.5 MHz,
2
C6D6): δ = 50.1 (CH2), 57.1 (dd, J = 2.2 Hz, J(C,P) = 22.5 Hz,
2
CH2), 61.6 (d, J(C,P) = 22.2 Hz, CH2), 127.6 (CAr), 128.1 (CAr),
4.11.1. Pt(5a)Cl2
128.5 (d, Cm-P, ,
3J(C,P) = 7 Hz, CAr), 128.7 (d, Cm-P 3J(C,P) = 7 Hz,
CAr), 127.6 (CAr), 128.0 (CAr), 128.5 (CAr), 129.6 (d, Co-P, d, 2J(C,P)
= 22 Hz, CAr), 129.7 (d, Co-P, d, 2J(C,P) = 22 Hz, CAr), 131.0 (q, d,
Colorless powder. 1H NMR (300 MHz, CDCl3): δ = 4.58 (2H,
s, CH2), 5.37 (2H, (d, 3J(H-P) = 17.0 Hz, CH2O), 6.42 (2H, d, J =
7.6 Hz, CHAr), 7.95-7.53 (m, 23 H, CHAr), ppm. 13C NMR (75.5
MHz, CDCl3): δ = 54.1 (CH2), 61.8 (CH2), 124.8 (q, CAr), 125.7
(q, CAr), 127.3 (CAr), 128.1 (d, J = 12.4 Hz, CAr), 128.4 (CAr),
128.5 (CAr), 128.7 (CAr), 128.8 (d, J = 12.6 Hz, CAr), 130.8 (q,
CAr), 131.8-132.0 (m, CAr), 132.1 (d, J = 12.0 Hz, CAr), 133.3 (q,
CAr), 150.9 (q, d, J = 18.2 Hz, CAr) ppm. 31P NMR (121.5 MHz,
2
J = 9.4 Hz, CAr), 134.1 (q, CAr), 139.9 (q, d, J(C,P) = 18.5 Hz,
2
CAr), 140.9 (q, d, J(C,P) = 18.5 Hz, CAr), 143.1 (q, d, J = 8.3 Hz,
CAr) ppm. 31P NMR (121.5 MHz, C6D6): δ = 128.9, 131.7 ppm.
MS (EI, 70 eV): m/z (%) = 588 (3) [M+1]+, 587 (4) [M]+, 386 (6)
[M-Ph2PO]+, 358 (29) [M-Ph2PO-N2]+, 201 (91) 91 (100).
HRMS (ESI) for C35H32N3OP2 found: 588.1973 [M+H]+, calcd.
588.1964 [M+H]+. HRMS (ESI) for C35H31N3NaOP2 found:
610.1788 [M+Na]+; calcd. 610.1784 [M+Na]+.
2
CDCl3): δ = -11.9 (dd, 1J(PPt) = 3726.8 Hz, J(PP) = 15.0 Hz), 91.2
1
2
(dd, J(PPt) = 3868.6 Hz, J(PP) = 15.0 Hz). HRMS (ESI) for
C34H29ClN3OP2Pt found: 788.11108 [M-Cl]+; calcd. 788.11171
[M-Cl]+, HRMS (ESI) for C34H29Cl2N3NaOP2Pt found:
846.07007 [M+Na]+, calcd. 846.06945[M+Na]+.
4.10.2.
1-Benzyl-4,5-bis[(dinaphtho[1,2-f:2´,1´d][1,3,2,]
dioxaphosphephin-4-yloxy)methyl]-1H-1,2,3-triazole (8b)
4.11.2. Pt(5b)Cl2

ACCEPTED MANUSCRIPT
10
Tetrahedron
1
Colorless powder. H NMR (300 MHz, CDCl3): δ = 2.19
128.3 (d, J = 12.3 Hz, CAr), 129.0 (CAr), 129.2 (CAr), 130.2 (q,
CAr), 131.2 (q, CAr), 131.8 (d, J = 2.9 Hz, CAr), 132.1 (d, J = 2.7
Hz, CAr), 132.2 (q, CAr), 132.5 (d, J = 11.5 Hz, CAr), 133.2 (d, J =
12.2 Hz, CAr), 138.4 (q, CAr), 150.6 (q, d, J = 19.2 Hz, CAr) ppm.
(3H, s, CH3), 4.50 (2H, s, CH2), 5.36 (2H, (d, J = 17.0 Hz, CH2),
6.33 (2H, d, J = 8.1 Hz, CHAr), 6.83 (2H, d, J = 8.0 Hz, CHAr),
7.12–7.53 (m, 20 H, CHAr), ppm. 13C NMR (75.5 MHz, CDCl3):
δ = 21.1 (CH3), 54.0 (CH2), 61.8 (CH2), 124.9 (q, CAr), 125.8 (q,
CAr), 127.5 (CAr), 128.1 (d, J = 12.2 Hz, CAr), 128.7 (CAr), 128.8
(d, J = 12.6 Hz, CAr), 129.2 (CAr), 130.3 (q, CAr), 130.8 (q, CAr),
131.8-132.0 (m, CAr), 132.1 (d, J = 12.0 Hz, CAr), 133.3 (d, J =
11.2 Hz, CAr), 138.4 (q, CAr), 150.9 (q, d, J = 18.0 Hz, CAr) ppm.
31P NMR (121.5 MHz, CDCl3): δ = -11.9 (dd, 1J(P2Pt) = 3726.8 Hz,
31P NMR (121.5 MHz, CDCl3): δ = 1.6 (d, J(PP) = 17.1 Hz),
2
2
120.6 (d, J(PP) = 17.8 Hz) ppm. MS (EI, 70 eV): m/z (%) = 342
(21.5) [M-Ph2PO-N2]+, 201 (40) [Ph2PO]+, 84 (100). HRMS
(ESI) for C35H31ClN3OP2Pd found: 712.0723 [M-Cl]+, cacld.
712.06698 [M-Cl]+.
2J(PP) = 15.0 Hz,), 91.2 (dd, J(PPt) = 3868.6 Hz, J(PP) = 15.0 Hz)
Acknowledgments
1
ppm. HRMS (ESI) for C35H31ClN3OP2Pt found: 802.12843 [M-
Cl]+, cacld. 802.12739[M-Cl]+.
The authors are grateful to by Evonik Oxeno GmbH for
financial support of this work. We thank Dr. C. Fischer, S.
Buchholz, A. Lehmann and K. Romeike (all at the Leibniz-
Institut für Katalyse e.V.) for their excellent analytical support.
4.11.3. Pt(8a)Cl2
Colorless powder. 1H NMR (300 MHz, CDCl3): δ = 4.73 (2H,
d, J = 8.4 Hz, CH2), 4.90 (2H, d, J = 7.8 Hz, CH2), 5.34 (2H, s,
CH2, CH2Ph), 6.95 (2H, d, J = 7.8 Hz, CHAr), 7.12-7.47 (m, 19 H,
CHAr), 7.61-7.70 (4H, m, CHAr) ppm. 13C NMR (75.5 MHz,
CDCl3): δ = 52.8 (CH2), 59.2 (d, J = 6.4 Hz, CH2), 60.8 (d, J =
7.3 Hz, CH2), 126.4 (CAr), 127.2 (d, J = 7.8 Hz, CAr), 127.4 (d, J
= 8.0 Hz, CAr), 127.7 (CAr), 127.8 (CAr), 128.1 (CAr), 129.4 (CAr),
129.6 (CAr), 130.2 (CAr), 130.3 (CAr), 130.4 (CAr), 130.6 (CAr),
131.0 (dd, J = 2.7 Hz, J = 12.0 Hz, CAr), 131.5 (d, J = 12.0 Hz,
CAr), 131.9 (d, J = 12.0 Hz, CAr), 132.7 (CAr), 142.5 (d, J = 8.8
Hz, CAr) ppm. 31P NMR (121.5 MHz, CDCl3): δ = 87.06 (dd,
1J(PPt) = 4187.9 Hz, 2J(PP) = 7.4 Hz,), 88.6 (dd, 1J(PPt) = 4216.9 Hz,
2J(PP) = 7.4 Hz) ppm. HRMS (ESI) for C35H31ClN3O2P2Pt found:
818.11312 [M-Cl]+, cacld. 818.11772 [M-Cl]+.
References and notes
1. Phosphorus(III) Ligands in Homogeneous Catalysis, Design and
Synthesis, P. C. J. Kamer, P. W. N. M. van Leeuwen (Eds.),
Wiley-VCH, 2012.
2. a) H. C. Kolb, M. G. Finn, B. K. Sharpless, Angew.Chem. Int. Ed.
2001, 40, 2004-2021; b) H. C. Kolb, B. K. Sharpless, Drug
Discovery Today 2003, 8, 1128-1137.
3. a) V. V. Rostovtsev, L. G. Green, V. V. Fokin, K. B. Sharpless,
Angew. Chem. Int. Ed. 2002, 41, 2596-2599; b) C. W. Tornøe, C.
Christensen, M. Meldal, J. Org. Chem. 2002, 67, 3057-3064; c) L.
V. Lee, M. L. Mitchell, S.-J. Huang, V. V. Fokin, K. B. Sharpless,
C.-H. Wong, J. Am. Chem. Soc. 2003, 125, 9588-9589; d) S. G.
Agalave, S. R. Maujan, V. S. Pore, Chem. Asian J. 2011, 6, 2696-
2718.
4. a) D. Liu, W. Gao, Q. Dai, X. Zhang, Org. Lett. 2005, 4907-4910;
b) Q. Dai, W. Gai, D. Liu, L. M. Kapes, X. Zhang, J. Org. Chem.
2006, 71, 3928-3934.
5. S.-i. Fukuzawa, H. Oki, M. Hosaka, J. Sugasawa, S. Kikuchi, Org.
Lett. 2007, 5557-5560.
6. R. J. Detz, S. Arevalo Heras, R. de Gelder, P. W. N. M. van
Leeuwen, H. Hiemstra, J. N. H. Reek, J. H. van Maarseveen, Org.
Lett. 2006, 8, 3227-3230.
7. a) E. M. Schuster, M. Botoshansky, M. Gandelman, Angew.
Chem. Int. Ed. 2008, 47, 4555-4558; b) E. M. Schuster, M.
Botoshansky, M. Gandelman, Organometallics 2009, 28, 7001-
7005; c) E. M. Schuster, G. Nisnevich, M. Botoshansky, M.
Gandelman, Organometallics 2009, 28, 5025-5031.
4.11.4. Pt(8b)Cl2
Colorless powder. 1H NMR (300 MHz, C6D6): δ = 5.30 - 5.76
(6H, m, CH2), 6.99-7.89 (m, 29 H, CHAr), ppm. 13C NMR (75.5
MHz, C6D6): δ = 53.3 (CH2), 56.3 (CH2), 59.8 (d, J = 4.2 Hz,
CH2), 125.3 (CAr), 127.2 (CAr), 127.7 (CAr), 128.2 (CAr), 128.6
(CAr), 128.7 (CAr), 129.2 (d, J = 12.4 Hz, CAr), 131.0 (d, J = 11.6
Hz, CAr), 131.5 (CAr), 131.9 (dd, J = 1.5 Hz, J = 8.6 Hz, CAr),
132.2 (dd, J = 1.6 Hz, J = 9.6 Hz, CAr), 133.1 (CAr), 137.8 (CAr),
142.3 (d, J = 3.3 Hz, CAr), 145.3 (d, J = 6.6 Hz, CAr), 145.6 (d, J
= 6.4 Hz, CAr), 146.3 (d, J = 12.0 Hz, CAr), 146.7 (d, J = 12.5 Hz,
8. F. Dolhem, M. J. Johansson, T. Antonsson, N. Kann, J. Comb.
Chem. 2007, 9, 477-486.
9. Y. Matano, M. Nakashima, A. Saito, H. Imahori, Org. Lett. 2009,
11, 3338-3341.
10. Q. Zhang, J. M. Takacs, Org. Lett. 2008, 10, 545-548.
11. In Ref. 7, among more than 20 phosphines-boranes also one BH3-
protected phosphine phosphite is mentioned.
12. (a) Rhodium Catalyzed Hydroformylation, van Leeuwen, P. W. N.
M.; Claver, C., Eds.; Kluver Academic Publishers: Dordrecht
Netherlands; 2000; (b) R. Franke, D. Selent, A. Börner, Chem.
Rev. 2012, 112, 5675–5732.
13. For reviews, see: a) S. Lühr, J. Holz, A. Börner, ChemCatChem
2011, 3, 1708-1730; b) Phosphorus Ligands in Asymmetric
Catalysis (Ed.: A. Börner), Wiley-VCH, Weinheim, 2008; c) N.
V. Dubrovina, I. A. Shuklov, A. Börner in Targets in Heterocyclic
Systems (Eds.: O. A. Attanasi, D. Spinelli), Royal Society of
Chemistry, Cambridge, 2008, vol. 12, 149-184. See also: a) I. A.
Shuklov, N. V. Dubrovina, E. Barsch, R. Ludwig, D. Michalik A.
Börner, Chem. Comm. 2009, 1535-1537; b) M.-N. Birkholz, N. V.
Dubrovina, H. Jiao, D. Michalik, J. Holz, R. Paciello, B. Breit, A.
Börner, Chem. Eur. J. 2007, 13, 5896-5907; c) N. V. Dubrovina, I.
A. Shuklov, M.-N. Birkholz, D. Michalik, R. Paciello, A. Börner,
Adv. Synt. Catal. 2007, 349, 2183-2187; d) N. Dubrovina, A.
Boerner, in Catalysts for Fine Chemical Synthesis (Eds.: S. M.
Roberts, J. Whittall) John Wiley&Sons Ltd., Chichester, 2007,
vol. 5, pp 89-93.
1
CAr), 31P NMR (121.5 MHz, C6D6): δ = 88.7 ppm (br. d, J(PPt)
=
=
2
1
2
5562 Hz, J(PP) = 24 Hz), 93.7 ppm (d, J(PPt) = 5542 Hz, J(PP)
24 Hz). HRMS (ESI) for C51H36Cl2N3O6P2Pt found: 1114.10878
[M+H]+, cacld. 1114.10963 [M+H]+.
HRMS (ESI) for
C51H36Cl2N3NaO6P2Pt found: 1136.09469 [M+Na]+, cacld.
1136.09157 [M+Na]+.
4.11.5. Synthesis of Pd(5b)Cl2 complex
To a stirred suspension of Pd(MeCN)2Cl2 (0.0571, 0.1 mmol)
in CH2Cl2 (1 mL) a solution of ligand 5b (0.0259 mg, 0.1 mmol)
in CH2Cl2 (2 mL) was added dropwise and the reaction mixture
was stirred for 2 h. The reaction mixture became homogeneous.
Then the solvent was evaporated and the obtained solid was dried
in vacuum. Yield was nearly quantitative. Lightly yellow
powder.
1H NMR (300 MHz, CDCl3): δ = 2.19 ( 3H, s, CH3), 4.54 (2H,
s, CH2), 5.28 (2H, (d, J = 16.8 Hz, CH2), 6.38 (2H, d, J = 8.0 Hz,
CHAr), 6.84 (2H, d, J = 7.9 Hz, CHAr), 7.14-7.62 (m, 20 H, CHAr)
ppm. 13C NMR (75.5 MHz, CDCl3): δ = 21.9 (CH3), 54.0 (CH2),
61.6 (d, J = 2.8 Hz, CH2), 125.4 (CAr), 126.3 (CAr), 127.6 (CAr),
14. For some recent examples, see: a) I. S. Mikhel, N. V. Dubrovina,
I. A. Shuklov, W. Baumann, D. Selent, H. Jiao, A. Christiansen,

ACCEPTED MANUSCRIPT
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Clkhmvsrcuionext.
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