P-Stereogenic Phosphonates via Dynamic Kinetic Resolution: A Route towards Enantiopure Tertiary Phosphine Oxides

Article abstract of DOI:10.1002/ejoc.201901475

Asymmetric synthesis of P-stereogenic phosphonates presents a great challenge. Following this target we disclose herein a DKR strategy towards the O–P coupling reaction between an easily accessible enantiopure phenol bearing a chiral sulfinyl auxiliary an

Full text of DOI:10.1002/ejoc.201901475

DOI: 10.1002/ejoc.201901475
Communication
Sulfoxides
P-Stereogenic Phosphonates via Dynamic Kinetic Resolution:
A Route towards Enantiopure Tertiary Phosphine Oxides
[
a]
[b]
[b]
[a]
Aabid Mohd, Thippani Anitha, Kallu Rajender Reddy, Joanna Wencel-Delord,* and
Françoise Colobert*[
a]
Abstract: Asymmetric synthesis of P-stereogenic phosphon- induction is achieved, several diastereopure phosphonates can
ates presents a great challenge. Following this target we dis- be afforded either by crystallization or flash chromatography.
close herein a DKR strategy towards the O–P coupling reaction Thus accessed optically pure P-stereogenic precursors may be
between an easily accessible enantiopure phenol bearing a chi- used as appealing building blocks to rapidly assembly original
ral sulfinyl auxiliary and a commercially available or easily acces- privileged scaffolds as illustrated via the synthesis of a chiral
sible racemic H-phosphinate. Although moderate to high chiral ligand such as PAMPO.
[
2g]
P-stereogenic organophosphorus compounds are an impor- the use of respectively a benzoxazaphosphinine-2 oxide and
[
8]
tant class of valuable products with widespread applications an oxaphospholidine obtained from
D
-glucosamine as chiral
particularly in asymmetric catalysis.[ Over the last twenty years phosphinyl transfer agents. Importantly an alternative protocol
1]
the synthesis of molecules with a P-stereogenic center has using enantioselective deprotonation of aryldimethyl phos-
[
2]
received significant attention. Accordingly, several modern phine boranes when using alkyllithium reagents in combination
approaches such as enantioselective metal-couplings and C–H with (–)-sparteine chiral ligand was disclosed by Evans
[
3]
[9]
activation based reactions have been reported. Besides, the (Scheme 1c).
development of chiral separation techniques provided an alter-
Regarding the great importance of P-stereogenic com-
[
4]
native approach. However, these transformations are gener- pounds in pharmaceutical and agrochemistry, but also their key
ally strongly limited by the generation of only specific P-stereo- importance in asymmetric synthesis, the development of new
genic scaffolds and/or are inadequate for a large-scale synthe- synthetic routes for the synthesis of P-stereogenic compounds
sis. Accordingly, diastereoselective synthesis of P-stereogenic is still a tempting challenge in organic chemistry. In particular,
compounds, calling for a use of an enantiopure auxiliary, is still designing a strategy towards a P-stereogenic “platform”, featur-
the most general and widely applied methodology to build up ingastrongmodularityandfacileconvertibilityintoanarrayofenan-
an array of P-stereogenic molecules. Indeed, already in 1967 tiopure molecules would be a significant advance. Following
Mislow had illustrated a great potential of cheap and abundant this challenge, enantioenriched P-stereogenic phosphonates
[
5]
menthol for the resolution of tertiary phosphines. Due to the bearing two different alkoxy substituents appear as excellent
versatility of this diastereoselective approach, this method candidates that could undergo the chemoselective and sequen-
greatly contributed to the design of P-stereogenic ligands such tial functionalization of both alkoxy substituents, paving the
as DiPAMP or Mini-Phos, and their applications in asymmetric way towards a broad array of enantiopure tertiary phosphine
[
6]
catalysis (Scheme 1a). Later Jugé showed that chiral amines oxides. Besides, the absolute configuration of the newly ac-
such as ephedrine were also very powerful chiral auxiliaries de- cessed scaffolds could also be controlled by a simple modifica-
livering the corresponding P-stereogenic oxazaphospholidine in tion of the order of the sequential functionalization. However
[
7]
high yield and diastereoselectivity (Scheme 1b). Similar strate- despite their great synthetic value, enantioenriched
3
1
2
gies developed by Han in 2013 and Framery in 2015 involved P(O)R (OR )(OR ) scaffolds remain elusive (Scheme 1d).
To address this synthetic challenge, we hypothesized that a
[
[
a] Laboratoire d'Innovation Moléculaire et Applications (UMR CNRS 7042),
direct and stereoselective O–P coupling could be envisioned
between a phenol bearing a chiral auxiliary in ortho-position
and a commercially available or easily accessible racemic H-
phosphinate as an organophosphorus precursor. Interestingly,
Université de Strasbourg / Université de haute Alsace, ECPM,
2
5 Rue Becquerel, 67087, Strasbourg, France
E-mail: francoise.colobert@unistra.fr
wenceldelord@unistra.fr
b] Catalysis and Fine chemicals Division, CSIR-Indian Institute of Chemical
Technology,
[
4b]
as H-phosphinates are prone to epimerisation,
such a cou-
pling could potentially occur via Dynamic Kinetic Resolution
Mechanism (DKR) thus allowing conversion of a racemic prod-
uct into a high value-added diastereoenriched P-compound. As
far as the choice of the chiral auxiliary is concerned, we sur-
mised that a sulfoxide moiety could be an efficient source of
Tarnaka, Hyderabad, Telangana State -500 007, India
E-mail: rajender@iict.res.in
rajenderkallu@gmail.com
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under https://doi.org/10.1002/ejoc.201901475.
Eur. J. Org. Chem. 0000, 0–0
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Communication
Scheme 1. Synthesis of P-stereogenic products.
chirality. Indeed, the sulfoxide auxiliary precursors 1) are retention of configuration on P atom, while the second step i.e.
straightforwardly accessible on large scale from cheap precur- nucleophilic substitution takes place with inversion of configu-
sors, 2) may be easily installed on the phenol coupling partner ration on P atom.
and 3) their high important optical stability under various con-
Following these considerations, we have designed phenols
ditions should warrant recycling of the phenol-sulfoxide motif 2A–C, bearing p-tolyl sulfinyl and the more hindered tert-butyl-
while performing final functionalization of the P-stereogenic sulfinyl and adamantly moieties respectively as chiral in-
product (Scheme 1e). Thus accessed optically pure phosphon- ductors for a diastereoselective O–P coupling reaction. Accord-
ates could potentially be transformed into a variety of original ingly the enantiopure phenols 2 bearing the sulfinyl auxiliary
P-stereogenic scaffolds by using organolithium or Grignard's re- were synthesized in high overall yields following a general strat-
agents with a concomitant release of the enantiopure phenol egy involving 1) the protection of o-bromophenol as a MOM
bearing chiral sulfoxide. Besides, if chiral phenol is used as the ether, 2) a bromine/ lithium exchange followed by condensa-
1
auxiliary, the diastereomeric P(O)R(OR )(OAr) obtained present tion with (S)-p-tolylmenthyl sulfinate (A), (S)-(tert-butyl)-tert-
two sites for further functionalization and if chemoselective butane thiosulfinate (B) or adamantan-1-yl-adamantane-1-sulf-
1
substitution of (OAr) and (OR ) can be conducted, a particularly inothioate (C) and finally 3) deprotection with HCl and crystalli-
large panel of P-stereogenic compounds could be accessed zation (Scheme 3).[12]
(
Scheme 1e).
With these chiral phenols in hand, we first performed the
Targeting the foreseen O–P couplings, we drew the inspira- coupling between the commercially available racemic ethyl-
tion from the Atherton Todd (AT) reaction, a classical synthetic phenyl H-phosphinate 1a and (S)-2-(p-tolylsulfinyl) phenol 2A.
method to prepare phosphoramidates, phosphonates and Under the standard reaction conditions, [1 equivalent of (S)-
other organophosphorus derivatives via X–P coupling between 2-(p-tolylsulfinyl) phenol 2A, 2 equivalents of triethylamine in
an organophosphorus precursor including H-phosphinate/H- carbon tetrachloride at room temperature under air] and using
phosphonate, and a nucleophile such as amine/alcohol. [10] This 2 equivalents of ethylphenyl H-phosphinate 1a, the desired O–P
reaction typically occurs in carbon tetrachloride and requires coupling reaction proceeded well, providing the corresponding
addition of a base, usually a trialkylamine. The (AT) reaction product 3aA in 83% isolated yield, but with a low 55:45 dia-
3
1
proceeds through inversion of configuration on P atom stereomeric ratio measured by P NMR of the crude reaction
[
11]
(
Scheme 2). Indeed the first step corresponds to the forma- mixture (Table 1, entry 1). Although the reaction is equally effi-
tion of a chlorophosphate intermediate and proceeds through cient at lower temperature, ie. –20 °C, no improvement in dia-
stereoselectivity was observed (Table 1, entry 2). This modest
chiral induction prompted us to use the more hindered (S)-2-
(
tert-butylsulfinyl)phenol 2B and its coupling with ethylphenyl
H-phosphinate 1a proceeded with full conversion furnishing
aB within 3 h and with an increased diastereomeric ratio of
3
Scheme 2. Atherton Todd reaction.
Eur. J. Org. Chem. 0000, 0–0 www.eurjoc.org
71:29 (entry 3). Detailed optimization of the reaction conditions
2
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Communication
revealed that: 1) the coupling was highly water-sensitive and this AT reaction we evaluated the potential of even more steri-
thus, the diastereoeselectivity was improved up to 83:17 while cally demanding phenol-sulfoxide 2C, bearing an adamantyl
adding molecular sieves (entry 4); 2) the replacement of toxic substituent at S-atom. Disappointingly, no improvement in the
CCl with THF, toluene, dioxane, Et O or DME in presence of chiral induction was observed, while the overall efficiency of
4
2
1
0 equivalents of CCl did not hamper the reactivity and full the coupling decreased (entry 16). Accordingly, under the
4
conversion of 1a to 3aB was observed despite a slightly de- optimized reaction conditions, that is, using 2 equivalents of
creased stereoselectivity (dr 77:23, entries 5–9). Of note is that racemic ethylphenyl H-phosphinate, 1 equivalent of enantio-
THF was selected as the solvent of choice for further screening pure (S)-2-(tert-butylsulfinyl)phenol, 10 equivalents of carbon
of the other reaction parameters; 3) decreasing reaction's con- tetrachloride, 4 equivalents of diisopropylethylamine and
centration positively impacted the chiral induction and the op- 75 mg/mL of molecular sieves (MS) in THF under argon at room
timal results in terms of efficiency and diastereoselectivity, ie. temperature for about 24 h, the maximum diastereomeric ratio
dr of 83:17 and full conversion within 2 h, were reached for a of 90:10 was achieved with 85% yield.
concentration of 0.05
M
(entries 10–11); 4) the use of 4 equiva-
Subsequently, we hypothesized that the low configurational
lents of diisopropylethylamine instead of Et N allowed to get stability of the H-phosphinates should facilitate their in situ
3
an excellent dr of 90:10 although prolonged reaction time up racemisation in the reaction mixture. Accordingly, the overall
to 24 h was required (entry 12). Of note is that other bases, transformation might occur via Dynamic Kinetic Resolution sce-
such as DBU, DMAP and 2,6-lutidine performed poorly (entries nario. In order to validate this assumption, this O-P coupling
13–15). Finally, to further increase the stereoinduction during was performed using equimolar amounts of 1a and 2B. As ex-
Scheme 3. Synthesis of enantiopure phenols 2.
Table 1. Atherton Todd O–P coupling reaction. Scheme of Table 1 in the middle of the page
Entry
1
R
Base
CCl
4
(x equiv.)
solvent
Y hours
Yield[a] [%]
dr
pTol
pTol
tBu
tBu
tBu
tBu
tBu
tBu
tBu
tBu
tBu
tBu
tBu
tBu
tBu
Adam
tBu
Et
Et
Et
Et
Et
Et
Et
Et
Et
Et
Et
3
3
3
3
3
3
3
3
3
3
3
N
N
N
N
N
N
N
N
N
N
N
–
–
–
–
CCl
CCl
CCl
CCl
4
4
4
4
24
24
3
2
1
1
1
1
1
2
6
24
1
2
2
24
24
90
90
55:45
58:42
71:29
83:17
77:23
77:23
77:23
77:23
77:23
83:17
83:17
90:10
50:50
50:50
–
[b]
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
> 95
> 95
> 95
> 95
> 95
> 95
> 95
> 95
90
> 95
> 95
85
0
67
[
c]
c
c
c
c
c
10
10
10
10
10
10
10
10
10
10
10
10
10
THF
Toluene
Et
2
O
dioxane
DME
THF
THF
THF
THF
THF
THF
THF
0[
1
2
3
4
5
6
7
c,d]
[c,e]
[c,d,f]
iPr
2
EtN
[c,d]
DBU
DMAP
lutidine
[c,d]
[c,e]
[c,d,f]
iPr
iPr
2
EtN
EtN
90:10
83:17
[c,d,f,g]
2
THF
80
1
[
a] yield determined by H NMR. [b] –20 °C. [c] With molecular sieves (75mg/mL). [d] 0.05
M. [e] 0.025
2
M. [f] iPr EtN (4 equiv.). [g] 1 equiv. of 1a was used.
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Communication
pected, we were delighted to obtain the desired product in
0% yield and 83:17 dr unambiguously suggesting the dynamic
Table 2. Scope for O-P coupling reaction.
8
kinetic resolution outcome (Table 1, entry 17). Changing several
reaction parameters did not allow improving the diastereo-
selectivity. This DKR scenario could be explained based on re-
cently reported DFT studies of the racemization of alkylphenyl
[
13]
H-phosphinates.
They proposed that in presence of an alco-
hol (i.e. our enantiopure ortho sulfinylphenol 2), pentavalent
intermediates may be generated allowing the racemization
through pseudorotation (Scheme 4).
Scheme 4. Speculative mechanism of the racemization of alkylphenyl H-phos-
phinates.
With the optimized conditions in hand, the scope of this
reaction was explored using different racemic H-phosphin-
[
4b,14]
[14f]
ates,
secondary phosphine oxides
as well as differently
[
12b]
substituted (S)-2-(tert-butylsulfinyl) phenols.
The AT reaction proceeds smoothly for a wide variety of
H-phosphinates as well as for the secondary phosphine oxides.
In general, as the steric hindrance of the alkoxy group attached
to P atom in H-phosphinates increases (3aB–3gB, Table 2),
yields and diastereoselectivities of the reaction decrease. More
sterically hindered H-phosphinates such as isopropyl-, cyclo-
hexyl-, tert-butyl-, and adamantylphenyl H-phosphinates were
converted into the corresponding AT products 3dB (64%, 77:23
dr), 3eB (67%, 60:40 dr), 3fB (60% NMR yield, 60:40 dr) and 3gB
(
68%, 50:50 dr) with lower yields and diastereoselectivities. Of
note is that this surprisingly low chiral induction observed for
the coupling of the adamantyl-substituted 1g does not arise
from the slow racemization of the H-phosphinate (increased
configurational stability of 1g at room temperature may be ex-
pected) as no improvement was reached when performing the
coupling in presence of 2 equivalents of 1g and decomposition
occured while conducting the reaction at 80 °C.
Next we explored the modification of the aromatic or ali- equally well, providing the corresponding products 3aD (64%,
phatic substituent attached to P atom in H-phosphinate. With 77:23 dr), 3aE (78%, 83:17 dr), 3bE (58%, 80:20 dr), 3dE (52%,
a naphthyl group the AT product 3hB was obtained in similar 79:21 dr) and 3aF (68%, 56:44 dr) bearing methoxy or bromine
yield and diastereomeric ratio (72%, 82:18 dr). However with substituent in ortho- or para-positions. Nevertheless, phenol
sterically hindered cyclohexyl group the yield decreased drasti- bearing a methyl group in ortho position was unreactive in this
cally and a slightly lower diastereoselectivity was obtained as O-P coupling, even at higher temperature, showing that the
well (3iB, 34%, 78:22 dr). Moreover, in case of ethyl methylphos- more hindered phenols were difficult to react with a H-phos-
phinate,1j, the corresponding product 3jB was furnished in phinate substrate. Secondary phosphine oxides also underwent
good yield and moderate diastereoselectivity (3jB, 80%, 70:30 the O-P coupling reaction smoothly delivering the correspond-
dr). Finally, substitution pattern of the phenol-sulfoxides 2 was ing products, 3kB (67%, 55:45 dr) and 3lB (75%, 51:49 dr) with
investigated. In case of substrates 2D–F, the reaction proceeded drastically lower diastereoselectivities.
Eur. J. Org. Chem. 0000, 0–0
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Communication
Subsequently, recrystallization of 3aB was targeted and a ration; this observation is consistent with the expected mecha-
monocrystal structure was obtained (Figure 1). Structural X-ray nism of the post-functionalization, occurring with inversion of
diffraction analysis allowed determination of the absolute con- the configuration at P-stereocenter. Besides, 2B was recovered
figuration of the major diastereomer as (S ,S ). The absolute as a single enantiomer in extremely high yield (94%).
S
P
configurations of other major diastereomers were attributed ac-
cordingly.
In summary we have developed a new diastereoselective
O-P coupling. The use of the sulfoxide as chiral auxiliary allows
performing this P–H functionalization under modified Ather-
ton–Todd conditions, at room temperature and in absence of a
catalyst. The diastereoselectivity observed is moderate to high
but the diastereomeric compounds may be separated in some
cases, thus providing optically pure P-stereogenic scaffolds. Im-
portantly, these new P-stereogenic scaffolds are interesting pre-
cursors for many other P-stereogenic molecules as post-modifi-
cations may be conducted. Accordingly, this new methodology
allows synthesis of PAMPO, the key precursor of P-stereogenic
ligands in very efficient and straightforward method.
S P
Figure 1. X-ray crystal structures of 3aB (S , S ).
Successively, our efforts have focused on post-modifications Acknowledgments
of these P-stereogenic compounds. Towards this goal both dia-
We thank the Indo-French Centre for the Promotion of Ad-
stereomers of 3gB were separated by silica gel chromatography
delivering the optically pure (S ,S )-3gB and (S ,R )-3gB in syn-
vanced Research (IFCPAR/CEFIPRA) for financial support. A. M.
is very grateful to CEFIPRA for a doctoral grant. We are also very
grateful to Dr. Lydia Karmazin et Dr. Corinne Bailly for single-
crystal X-ray diffraction analysis.
S
P
S P
thetically useful yields (33 and 35% yield of each diastereomer).
With the diastereomerically pure P-precursors in hand, the post-
functionalization was attempted, using MeMgBr as nucleophile.
Rewardingly, fully chemoselective transformation took place as
selective cleavage of the sulfoxyde-phenyl 2B occured, deliver-
ing 4 in 64% yield and 90:10 er. Importantly, the chiral auxiliary
Keywords: P-stereogenic phosphonate · O–P coupling ·
Sulfoxide · Dynamic kinetic resolution · Tertiary phosphine
oxide
2
B could be recovered in 93% yield and excellent optical purity
(ee 99:1) (Scheme 5).
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Communication
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Communication
Sulfoxides
A. Mohd, K. R. Reddy, J. Wencel-Delord,*
F. Colobert* .......................................... 1–7
P-Stereogenic Phosphonates via Dy-
namic Kinetic Resolution: A Route
towards Enantiopure Tertiary Phos-
phine Oxides
A DKR scenario towards O–P coupling genic phosphonates bearing two dif-
reaction involving an easily accessible ferent alkoxy groups are valuable pre-
enantiopure phenol bearing a chiral cursors to reach privileged ligands
sulfinyl auxiliary and racemic H-phos- such as PAMPO.
phinates. The enantiopure P-stereo-
DOI: 10.1002/ejoc.201901475
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim