Substitution- and elimination-free phosphorylation of functionalized alcohols catalyzed by oxidomolybdenum tetrachloride

Article abstract of DOI:10.1002/adsc.200900279

Among 14 oxidometallic species examined for catalytic phosphorylation of the tested alcohols, oxidomolybdenum tetrachloride (MoOCl₄) was found to be the most efficient with a negligible background reaction mediated by triethylamine (Et₃N). The new catalytic protocol can be applied to the chemoselective phosphorylations of primary, secondary and tertiary alcohols as well as the substitution-free phosphorylations of allylic, propargylic, and benzylic alcohols. Functionalized alcohols bearing acetonide, tetrahydropyranyl ether, tert-butyldimethylsilyl ether, or ester group are also amenable to the new catalytic protocol. The most difficult scenarios involve substitution-free phosphorylations of 1-phenylethanol and 1-(2-naphthyl)ethanol which can be effected in 95 and 90% yields, respectively. ESI-MS, IR, ¹H, and ³¹P NMR spectroscopic analyses of the reaction progress suggest the intermediacy of an alkoxyoxidomolybdenum trichloride-triethylamine adduct such as [(RO)Mo(O)Cl₃-Et₃N] to be responsible for the catalytic turnover.

Full text of DOI:10.1002/adsc.200900279

FULL PAPERS
DOI: 10.1002/adsc.200900279
Substitution- and Elimination-Free Phosphorylation of Function-
alized Alcohols Catalyzed by Oxidomolybdenum Tetrachloride
Cheng-Yuan Liu,a,b Vijay D. Pawar,a,b Jun-Qi Kao,a and Chien-Tien Chena,*
a
Department of Chemistry, National Taiwan Normal University, Taipei, Taiwan, Republic of China
Fax : (+886)-2-2932-4249; phone: (+886)-2-2930-9095 ext. 121; e-mail: chefv043@ntnu.edu.tw
Cheng-Yuan Liu and Vijay D. Pawar made equal contributions to this work.
b
Received: April 21, 2009; Revised: November 9, 2009; Published online: December 16, 2009
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/adsc.200900279.
Abstract: Among 14 oxidometallic species examined tution-free phosphorylations of 1-phenylethanol and
for catalytic phosphorylation of the tested alcohols, 1-(2-naphthyl)ethanol which can be effected in 95
1
oxidomolybdenum tetrachloride (MoOCl4) was and 90% yields, respectively. ESI-MS, IR, H, and
found to be the most efficient with a negligible back- 31P NMR spectroscopic analyses of the reaction prog-
ground reaction mediated by triethylamine (Et3N). ress suggest the intermediacy of an alkoxyoxidomo-
The new catalytic protocol can be applied to the che- lybdenum trichloride-triethylamine adduct such as
moselective phosphorylations of primary, secondary [(RO)Mo(O)Cl3-Et3N] to be responsible for the cata-
and tertiary alcohols as well as the substitution-free lytic turnover.
phosphorylations of allylic, propargylic, and benzylic
alcohols. Functionalized alcohols bearing acetonide,
tetrahydropyranyl ether, tert-butyldimethylsilyl ether, Keywords: catalysis; chemoselectivity; diphenyl
or ester group are also amenable to the new catalytic phosphates; oxidometallic species; sensitive benzyl
protocol. The most difficult scenarios involve substi- phosphates
Introduction
scavenger like pyridine[7] or triethylamine.[8] Alterna-
tively, the use of N,N-dimethylaminopyridine
Phosphoryl group transfer to a given protic nucleo- (DMAP) as a nucleophilic catalyst was also report-
phile constitutes an important process towards the ed.[9] Transition metal catalysts such as Cu(II),
synthesis of biologically active molecules. Many im- LaACHTUNGTNRE(UNNG III), FeACHUTNTGERNNUG(III), CrACHUTNGERTGUN(NN III), Ti(IV), Zr(IV), YACHTGUNTREN(NNGU III), and
portant bioactive components in nature contain phos- Sn(IV) have been widely employed for the hydrolysis
phate esters. Major proteins of bone, teeth, eggs, and of phosphonates, fluorophosphates, and phosphate
milk are also enriched with phosphates. Glycosides/ esters.[10] However, relatively fewer efforts have been
glycoproteins possessing phosphate ester residues are devoted to studies of the catalytic phosphorylation of
mostly found as a component of the cell wall and are alcohols. One seminal methodology was reported with
implicated in many biological processes such as regu- the use of bis(2-oxo-3-oxazolinyl)phosphinate as the
lating immune response and tumor metastasis.[1] Phos- phosphoryl source in a catalytic fashion by Zr(IV).[11]
phorylated natural products like d-myo-inositol 1- Very recently, Jones and co-workers realized such a
[12]
[13]
phosphate[2] have been shown to play an imperative transformation by using TiCl4,
Ti
(OTf)2 with chlorophosphates or N-phosphorylox-
azolidinone in the presence of a stoichiometric
(OTf)2 in combina-
bifunctional imidazole and metal
plished by oxidation of moisture-sensitive PACUTHGNTRNENU(NG III) inter- hexafluorophosACHTUNGTRENpNUGN hate salts were also examined for al-
G
and
role in regulating transmembrane signalling.[3]
CuACHTUNTGRENNUNG
A tremendous amount of work has been reported
ACHTUNGTRENNUNG
for the preparation of phosphate esters.[4] Introduction amount of Et3N.[14] In addition, Mg
ACHTUNGTRENNUNG
of phosphate ester groups was sometimes accom- tion with
a
mediates to the corresponding O=P(V) analogues. cohol phosphorylation in the presence of Et3N.[15] No-
Besides, milder methods include reactions of chloro- tably, these catalytic systems involve the use of strong
phosphates with lithium or thallium alkoxides[5,6] or Lewis acids. As part of our ongoing programs utilizing
À
with straight alcohols in the presence of a proton oxidometallic species in the catalysis of C C and C
188
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Substitution- and Elimination-Free Phosphorylation of Functionalized Alcohols
X bond formation,[16] we sought to evaluate the feasi- nificant improvement in chemical conversions over
bility of catalyzing the phosphorylation event by using those from the background reactions mediated by
neutral, amphoteric, and water-tolerant oxidometallic Et3N. In marked contrast, group VIB oxidometallic
species. Herein we disclose our preliminary finding to- species except WO2Cl2 and MoO CHTUGNTERNN(UNG acac)2 exhibit sig-
2A
wards this end.
nificant conversion increments (entries 10–14). Nota-
[17]
bly, MoO2Cl2
and MoOCl4 were found to be the
most promising catalysts particularly for the phos-
phorylation of 28 alcohols (76 and 81% yields). Con-
versely, the use of MoCl5 led to only 54% yield for 2,
Results and Discussion
We began our investigation with an extensive survey indicating the unique role of the oxidomolybdenum
of various oxidometallic species as catalysts from unit(s) in the catalytic process.
groups IVB-VIB with benzyl alcohol and cyclohexa-
To further differentiate the catalytic function from
nol as representative primary (18) and secondary (28) the background intervention, we performed both the
substrates, respectively. The test phosphorylations optimal catalytic reactions and the background reac-
were carried out by using ClP(O)ACTHNUTRGENUG(N OPh)2 in the pres- tion at 08C on the test alcohols (entries 16–18). It was
ence of Et3N (1 equiv.) in CH2Cl2 and were stopped found that the phosphorylation of cyclohexanol is es-
within the same period of reaction time (i.e., 1 hour). sentially silent in the background at 08C. Conversely,
The extent of background phosphorylation without MoOCl4 (42% yield) shows significantly better perfor-
any catalyst was also quantified to be 62% and 25%, mance than MoO2Cl2 (14% yield) at 08C for the same
respectively, as shown in entry 1 (Table 1). It was process. Therefore, the operating role of MoOCl4 as
found that oxidometallic species from group IVB the best catalyst is confirmed. By systematically vary-
[e.g., TiOACHTUNGTRENNUNG(acac)2, TiOCl2, ZrOCl2, and HfOCl2] tend ing the catalyst loadings, we also found that 10 mol%
to slow down or completely suppress the conversion is optimal in terms of reaction conversion in 1
of the starting alcohols to the corresponding phos- hour.[18] Notably, MoOCl4 can even be recovered as
phate products 1 and 2 (entries 2–5). Among mem- the MoOCl3ACHTUNTRGNEUNG(OCH2Ph)-NEt3 and MoOCl4-NEt3 ad-
bers in group VB (entries 6–9), only VCl3 shows sig- ducts (91–95% recovery yield) from the aqueous
layer and re-used with 84–93% of the original catalyt-
ic efficiency for four consecutive runs.[19] Among
seven organic and two inorganic bases examined,
Et3N (entry 1) remains the most appropriate base for
Table 1. Catalyst screening for the tested phosphorylation of
benzyl and cyclohexyl alcohols.
the catalytic phosphorylation of cyclohexanol
(Table 2). Further optimization of the reaction condi-
tions and solvent led to the recipe of 1.2 equivalents
of diphenyl chlorophosphate, 1.2 equivalents of Et3N,
and 10 mol% of MoOCl4 in CH2Cl2 at ambient tem-
perature.
The optimal catalytic system was then applied to
the phosphorylation of various 18–38 alcohols and
phenolic alcohols (Table 3 and Table 4).[20] In general,
primary alcohols can be transformed to the corre-
sponding phosphates in excellent isolated yields (88–
Entry
Catalyst
none
% Conv. of
% Conv. of
18 ROH[a]
28 ROH[a]
1
2
3
4
5
6
7
8
62
71
24
29
24
62
90
52
29
90
37
83
90
57
49
14
14
52
25
31
trace
trace
trace
22
63
44
17
62
trace
76
81
47
54
trace
14
42
TiO
N
TiOCl2
ZrOCl2
HfOCl2
VOACHTUNGTRENNUNG(OTf)2
VCl3
Table 2. Effect of bases on the catalytic phosphorylation of
cyclohexanol by MoOCl4.
VOCl3
9
VO
N
Entry
Base
Et3N
AHCTUNGTERNN(GUN i-Pr)2NEt
quinuclidine
DABCO
DBU
pyridine
2,6-lutidine
NaOAc or K2CO3
none
% Conversion[a]
10
11
12
13
14
15
16
17
18
WOCl4
WO2Cl2
MoO2Cl2
MoOCl4
1
2
3
4
5
6
7
8
9
81
58
51
23
19
13
12
0
MoO
N
MoCl5
none (at 08C)
MoO2Cl2 (at 08C)
MoOCl4 (at 08C)
0
[a]
Conversions calculated from integration values in the
1H NMR spectrum.
[a]
Determined by 1H NMR.
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Table 3. Catalytic phosphorylation of various 18 alcohols by MoOCl4.[a]
Entry
Starting alcohol
Time [h]
Yield [%][b]
1
2
3
4
5
PhCH2OH
PhCH2CH2OH
Cl-(CH2)2OCH2CH2OH
H2C=CHACHTUNGTRENUNG(CH2)2CH2OH
1
1
1
1
1
98 (1)
99 (3)
97 (4)
99 (5)
99 (6)
H2C=CHCH2OH
6
1
88 (7)
ꢀ
7
8
HC CHCH2CH2OH
1
1
95 (8)
99 (9)
ꢀ
HC CHCH2OH
9
1
89 (10)
10
11
1
1
94 (11)
92 (12)
12
13
TBSO
THPOAHCTNUGTRENNNUG
G
1
1
98 (13)
92 (14)
[a]
Reactions performed with 1.2 equiv. of ClP(O)
temperature.
Isolated, pure product yields after column chromatography.
ACHTUGNRTNE(NUGN OPh)2, 1.2 equiv. of Et3N, and 10 mol% of MoOCl4 in CH2Cl2 at room
[b]
99%) in 1 h (entries 1–13, Table 3). Activated alcohols due to increased steric effects. Notably, no elimination
like benzylic (entry 1), allylic (entries 5 and 6), prop- by-product of the phosphate 17 was observed under
argylic (entry 8), and an SN2 sensitive one (entry 3) the reaction conditions (entry 4, Table 4). Phenolic
are tolerated. No signs of etherification between the substrates were easily phosphorylated (92–98%
starting alcohol and the corresponding phosphate yields) in 1 hour with negligible electronic effects of
product were observed in all cases. The current cata- the para-substituents (entries 5–7, Table 4).
lytic protocol tolerates ethylene glycol and ester func-
Notably, the most challenging phosphorylations of
tionalities (entry 9) as illustrated in the phosphoryla- 1-phenylethanol and 1-napthalen-2-ylethanol (en-
tion of methyl gallate bearing diethylene glycol termi- tries 8 and 9) were accomplished in 3 h with quantita-
1
nals. Notably, the phosphorylated product 10 may act tive conversions as judged by H NMR and in 95%
as an important building block towards hydrophilic and 90% isolated yields, respectively. No etherifica-
nanohybrids.[21] Furthermore, the functional group tion or chlorination product resulting from the nucle-
compatibility of the new catalytic system was illustrat- ophilic attack of 21a, b by chloride or the starting al-
ed by its applications to alcohols bearing Lewis acid- cohol was observed. To the best of our knowledge,
sensitive components such as acetonide (entries 10 this represents one of the most successful catalytic
and 11), glycosidic acetal (entry 11), tert-butyldime- systems[15] that can achieve the syntheses of 21a and
thylsilyl (TBS) (entry 12), and tetrahydropyranyl 21b in high yields. Substrates derived from natural
(THP) ethers (entry 13).
sources like cholesterol, diacetonide-d-glucose, iso-
Furthermore, simple secondary alcohols can be borneol, and menthol can also be smoothly phos-
readily phosphorylated in 90–95% yields (entries 1–3, phorylated in 90–92% yields (entries 10–13, Table 4)
Table 4) in 1–1.5 h. It takes slightly longer (3 h) for a albeit with longer reaction times (8–24 h). The ability
28 alcohol bearing two flanking benzyl groups of tolerating Lewis acid-sensitive groups was again
(entry 4) to be completely phosphorylated, presumbly demonstrated in the case of diacetonide-d-glucose
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Substitution- and Elimination-Free Phosphorylation of Functionalized Alcohols
Table 4. Catalytic phosphorylation of various 2–38 and phe-
nolic alcohols by MoOCl4.[a]
Entry Starting alcohol
Time [h] Yield [%][b]
1
2
CH3CH(OH)CH2CH3
cy-C6H11OH
1
1.5
95 (15)
90 (2)
3
1
90 (16)
4
3
90 (17)
5
6
7
C6H5OH
4-NO2C6H4OH
4-CH3OC6H4OH
1
1
1
98 (18)
92 (19)
92 (20)
8
3
95 (21a)[c]
9
3
90 (21b)[c]
Scheme 1. Top : Chemoselective phosphorylation. Bottom:
Intermolecular competitive phosphorylation between a 28
and a 38 alcohol.
10
11
14
24
92 (22)
90 (23)
methyl (O2,O3-dibenzoyl-a-d-glucopyranoside). The
reaction was complete in 2 h leading to product 29
with exclusive phosphorylation at the primary, C6-hy-
droxy group in 94% yield along with recovery of the
remaining starting material in 5% yield, Scheme 1. To
the best of our knowledge, this is the first successful
example for this type of substrate. Furthermore, an
intermolecular competition experiment for the che-
moselective phosphorylation of a 1:1 mixture of cyclo-
hexanol and tert-butanol under the standard catalytic
protocol led to only cyclohexyl diphenyl phosphate 2
in 99% yield.
Since MoOCl4 and MoO2Cl2 are catalytically more
active than MoCl5, we speculate that ClP(O)ACTHNURGTNEUNG(OPh)2 is
activated by its coordination to the Mo=O unit, lead-
ing to an adduct Ia (Scheme 2). ESI-MS analysis
(CH3CN as the eluent) of a 1/1 mixture of MoOCl4/
12
13
10
8
90 (24)
92 (25)
14
15
16
N
30
30
30
96 (26)
92 (27)
90 (28)
H-C C C
CH3CH2-CACHTUNGTRENNUNG
ACHTUNGTRENNUNG
[a]
Reactions performed with 1.2 equiv. of ClP(O)ACTHUNRGTNEUNG(OPh)2,
1.2 equiv. of Et3N, and 10 mol% of MoOCl4 in CH2Cl2 at
room temperataure.
ClP(O)ACTHNUTRGNE(UNG OPh)2 in CD2Cl2 reveals of the existence of
[b]
[c]
Isolated, pure product yields after column chromatogra-
Ia which supports this presumption. The IR spectrum
of the same solution mixture shows a shift of the P=O
signal from 1310 to 1280 cmÀ1 and the Mo=O signal
remains intact without any discernible signal related
phy.
Product unstable to silica gel and 2 equiv. of Et3N were
used.
À1 [19,22]
À
Mo O stretching around 800–900 cm .
Further
supportive insights were provided by 1H NMR studies.
(entry 11). The phosphorylated product 23 was isolat- After addition of MoOCl4 into ClP(O)
ed in 90% yield without glycosidic acetonide opening ratio) in CD2Cl2, the signal at d=7.44 ppm was shift-
or acetonide migration. ed upfield to d=7.42 ppm, and the one at d=
ACHTUNGRTENN(UNG OPh)2, (1:1
To extend the substrate scope of the new catalytic 7.31 ppm was downfield shifted to d=7.32 ppm
protocol, three representative tertiary alcohols were (Figure 1). The chemical shift change profile is similar
further examined (entries 14–16, Table 4). It was to that upon mixing MoOCl4 and P(O)
found that all these reactions proceeded cleanly in ratio). Therefore, the alternative, nucleophilic acyl
90–96% isolated yields in 30 h, which were by far not substitution of ClP(O)(OPh)2 by MoOCl4 to form
adduct Ib is ruled out (Scheme 2). In addition,
ACHTUNGRTENN(UNG OPh)3 (1:1
AHCTUNGTRENNUNG
equaled by other catalytic systems.
As a final demonstration regarding the utility of 31P NMR analysis for the same mixture in CD2Cl2 led
the new catalytic protocol, we have performed a che- to complete formation of only one downfield signal at
moselective phosphorylation of a monosaccharide – d=À3.19 ppm as compared to that of the original
Adv. Synth. Catal. 2010, 352, 188 – 194
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Cheng-Yuan Liu et al.
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Scheme 2. Proposed mechanism for the catalytic phosphorylation by MoOCl4.
Figure 1. 1H NMR spectroscopic analyses for ClP(O)
ACHTUNRGTNEUNG(OPh2)2 in CD2Cl2 before (top) and after (bottom) addition of 1 equiva-
lent of MoOCl4.
ClP(O)
(OPh)2 at d=À5.13 ppm, which is consistent
ESI-MS analysis (CH3CN as the eluent) of an ali-
with the findings from ESI-MS, IR, and 1H NMR quot from a catalytic reaction mixture with benzyl al-
analyses.[19]
cohol in CD2Cl2 suggests the formation of an adduct
between Cl3Mo(O)ACTHNUGTRNE(UGN OCH2Ph) and NEt3 (i.e., adduct
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Substitution- and Elimination-Free Phosphorylation of Functionalized Alcohols
including Lewis acid-sensitive glycosidic acetal, aceto-
nide, silyl, and THP ether units. Furthermore, this
new catalytic protocol represents a mild and practical
synthetic approach to effect the phosphorylation of
substrates that are sensitive to intervening substitu-
tion or elimination and to access phosphates derived
from sterically hindered alcohols in high yields. Gly-
cosides bearing Lewis-acid labile groups can also be
smoothly phosphorylated. Chemoselective phosphory-
lation can be achieved in an intramolecular or inter-
molecular diol system. ESI-MS, IR, 1H NMR, and
31P NMR spectroscopic analyses of the reaction mix-
ture with PhCH2OH before, during, and after the
phosphorylation indicate the Lewis acid nature of
MoOCl4 and the intermediacy of (PhCH2O)MoOCl3-
Et3N (i.e., adduct III). Further studies are underway
to expand the scope of the catalytic process to asym-
metric variants and alcohol substrates of biological in-
terest.
Experimental Section
General Procedure for Catalyst Screening
Catalyst (10 mol%) was stirred in CH2Cl2 (5 mL) at room
temperature under nitrogen. A solution of a given alcohol
in CH2Cl2 (5 mL) was added followed by Et3N (1.0 equiv.)
Figure 2. ESI-mass spectrum of the adduct III.
and ClP(O)ACTHNUGRTENUNG(OPh)2 (1.0 equiv.). The resulting mixture was
stirred at room temperature for 1 hour and then quenched
with distilled water (10 mL). The aqueous layer was separat-
ed and extracted with CH2Cl2 (3ꢁ10 mL). The combined or-
ganic layers were dried (MgSO4), filtered, and concentrated.
The reaction conversion was determined by integration
ratios of the protons of C-1 with attached OH in the alcohol
III) even after completion of the reaction (Figure 2).
A series of 31P NMR analyses for the same mixture in
CD2Cl2 with time showed only the signal for
ClP(O)
A
tensity and an increasing, broad product signal at d=
À11.39 ppm.
1
and C-1 in the phosphate, respectively, in the H NMR spec-
tra.
Conversely, the original catalyst (MoOCl4-L, L=
CH3CN and/or Et3N) was detected in negligible
amounts during the the course of the reaction. Since
the catalytic reaction cannot proceed in the absence
of Et3N and the original catalyst is present in a mini-
mal amount or is short-lived during the reaction, the
initial adduct Ia may undergo subsequent reaction
with an alcohol (e.g., PhCH2OH) in the presence of
Et3N. The resultant Mo-bound alkoxide IIa
(31P NMR: d=À11.45 ppm) would further undergo
phosphorylation either in an inter- or intramolecular
fashion with concomitant release of MoOCl4-L. A re-
siding and turnover species III is formed once
MoOCl4-L further reacts with a given alcohol in the
presence of Et3N.
Representative Procedure for the Phosphorylation of
Alcohols
In a 25-mL, two-necked, round-bottomed flask was placed
the alcohol (0.1 mmol) in CH2Cl2. To the reaction flask was
added MoOCl4 (10 mol%), Et3N (0.12 mmol, 1.2 equiv.),
and ClP(O)ACTHNUGTRENUNG(OPh)2 (0.12 mmol, 1.2 equiv.) at ambient tem-
perature. The reaction mixture was stirred for the designat-
ed time as evidenced by TLC analysis and then quenched
with distilled water (10 mL). The aqueous layer was separat-
ed and extracted with CH2Cl2 (3ꢁ10 mL). The combined or-
ganic layers were dried (MgSO4), filtered, and concentrated.
The crude residue was purified by column chromatography
on silica gel to provide the pure diphenyl phosphate prod-
uct.
Conclusions
Acknowledgements
We have developed a new and highly potent phos-
phorylation catalyst, MoOCl4, that is compatible with
We thank the National Science Council of Taiwan for gener-
substrates possessing a wide range of functionalities ous financial support of this research.
Adv. Synth. Catal. 2010, 352, 188 – 194
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Cheng-Yuan Liu et al.
FULL PAPERS
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[20] The new catalytic protocol can also be applied to the
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