Application of chiral 2-isoxazoline for the synthesis of syn-1,3-diol analogs

Article abstract of DOI:10.3762/bjoc.15.179

The asymmetric cycloaddition of TIPS nitronate catalyzed by “Cu(II)-bisoxazoline” gave the 2-isoxazoline product in 95% yield, which was converted into tert-butyl (3S,5R)-6-hydroxy-3,5-O-isopropylidene-3,5-dihydroxyhexanoate in 14 steps through a β-hydroxy ketone.

Full text of DOI:10.3762/bjoc.15.179

Application of chiral 2-isoxazoline for the synthesis of
syn-1,3-diol analogs
Juanjuan Feng, Tianyu Li, Jiaxin Zhang* and Peng Jiao*
Letter
Open Access
Address:
Beilstein J. Org. Chem. 2019, 15, 1840–1847.
Key Laboratory of Radiopharmaceuticals, College of Chemistry,
Beijing Normal University, Beijing 100875, P.R. China
doi:10.3762/bjoc.15.179
Received: 17 April 2019
Accepted: 12 July 2019
Published: 01 August 2019
Email:
Jiaxin Zhang* - zhangjiaxin@bnu.edu.cn; Peng Jiao* -
pjiao@bnu.edu.cn
Associate Editor: T. P. Yoon
* Corresponding author
© 2019 Feng et al.; licensee Beilstein-Institut.
License and terms: see end of document.
Keywords:
β-hydroxy ketone; cycloaddition; 1,3-diol; isoxazoline; silyl nitronate
Abstract
The asymmetric cycloaddition of TIPS nitronate catalyzed by “Cu(II)-bisoxazoline” gave the 2-isoxazoline product in 95% yield,
which was converted into tert-butyl (3S,5R)-6-hydroxy-3,5-O-isopropylidene-3,5-dihydroxyhexanoate in 14 steps through a
β-hydroxy ketone.
Introduction
The chiral 1,3-diol structure is widespread in a broad spectrum pioneered by Wong [42], is equally competitive. Here, we
of natural products [1,2]. (3R)-β-Hydroxy-δ-lactone or its open- report the preparations of tert-butyl (3S,5R)-6-hydroxy-3,5-O-
ring equivalent (3R)-syn-3,5-dihydroxypentanoic acid, is a isopropylidene-3,5-dihydroxyhexanoate and related syn-1,3-diol
common structure in naturally occurring mevastatin (or analogs from a chiral 2-isoxazoline (Scheme 1b). This work is
compactin), lovastatin or closely related statins, and synthetic part of our continuous efforts in asymmetric syntheses and ap-
statins. Either the syn or anti-1,3-diol could be prepared from plications of chiral 2-isoxazolines [49-51].
enantiomerically pure β-hydroxy ketones through β-hydroxy-
directed carbonyl reduction following Evans’ [3] or Prasad’s Results and Discussion
[4-11] method. The Narasaka–Prasad reduction of a δ-hydroxy- Our synthesis commenced with a chiral 3,5-disubstituted-2-
β-keto esters derived from β-hydroxy esters [12-23] is widely isoxazoline 3 or 4, which were prepared from silyl nitronate
used to prepare tert-butyl (3R)-3,5-O-isopropylidene-3,5-dihy- through an asymmetric 1,3-dipolar cycloaddition developed in
droxyhexanoate (Scheme 1a) [24-37], which is a building block our lab (Table 1) [49]. The synthesis of the triisopropylsilyl
for synthetic statins [38-41], though enzymatic syntheses [42- nitronate was initially attempted starting with 3-nitropropionic
48] of the chiral β-hydroxy-δ-lactone moiety or its equivalents, acid methyl ester but no desired product was observed. How-
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Beilstein J. Org. Chem. 2019, 15, 1840–1847.
Scheme 1: Accesses to tert-butyl 3,5-O-isopropylidene-3,5-dihydroxyhexanoates. (a) Previous methods using Claisen condensation. (b) Our new
method using cycloaddition.
Table 1: Optimization of the conditions for the asymmetric cycloaddition.
Entry
Ligand
x mol % Cu
T (°C)
Yield (%) (1)
ee (%) (4)
1
2
3
4
5
6
A
A
B
B
B
B
10
20
10
20
20
20
−50
−50
−50
−50
−40
−60
25
75
70
95
78
84
18
72
66
80
78
80
ever, switching to 3-nitropropanol, protected as the THP ether, previous ligand screening results [49], two bisoxazolines with
succeeded to prepare the required triisopropylsilyl nitronate. an isopropyl (ligand B) or tert-butyl group (ligand A) were
Then, the catalytic asymmetric cycloaddition gave the 2-isoxa- tested. Optimization of the conditions established that 26 mol %
zolidine cycloadduct 1 in a high yield. In the light of our of ligand B together with 20 mol % Cu(OTf)2 in anhydrous
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CH2Cl2 catalyzed the cycloaddition between N-acryloyl-1,3- this method to deprotect the isoxazoline 3. However, the desired
oxazolidin-2-one and the silyl nitronate at −50 °C to give 1 in β-hydroxy ketone was never obtained. In one instance, the
95% isolated yield, which subsequently generated 3,5-disubsti- methyl ketone from a retro-aldol reaction of the desired
tuted isoxazoline 4 in 80% ee. Decreasing the amount of the β-hydroxy ketone was observed. In our experience, the hydro-
chiral Lewis acid catalyst led to a decrease of both the ee and genolysis of a 2-isoxazoline having a 5-ester group was trouble-
the yield. Desilylation of the 2-isoxazolidine 1 was effected in some. Thus, the 5-ester group was reduced with NaBH4 to give
CHCl3 using catalytic amounts of p-toluenesulfonic acid 5. The hydroxy group was subsequently protected with benzoyl
(PTSA). Though the yield of the in situ-generated 2-isoxazo- (Scheme 3), which also worked as a chromophore facilitating
line 2 bearing the 1,3-oxazolidin-2-one auxiliary was perfect, HPLC analysis. Afterwards, we tried oxidations once again.
purification of 2 by silica gel chromatography was problematic After removal of THP from 6, the resulting compound 6' was
due to decomposition. No pure product was isolated from crude subjected to oxidation with various reagents (Scheme 4) [53-
2 by chromatography on silica gel. Decomposition occurred to a 55]. The expected carboxylic acid or aldehyde was not ob-
compound similar to 2, in which the 3-substituent was CH2OH served, which further verified the intolerance exemplified in
[49]. To overcome this problem, the crude reaction mixture Scheme 2. These results prompted us to try the oxidation in a
containing 2 and PTSA was concentrated before excess Et3N later stage.
was added followed by CH3OH as the solvent. These opera-
tions removed the 1,3-oxazolidin-2-one auxiliary while When 6 was subjected to Raney-Ni-catalyzed hydrogenolysis,
preserving the THP group, and afforded the corresponding the desired β-hydroxy ketone 7 was obtained in 85% yield
methyl ester 3 (Table 1), which was stable and could be subject- (Scheme 3). Under the weakly acidic conditions, the THP group
ed to silica gel chromatography. Compound 4 was used to de- survived. Next, a Narasaka–Prasad reduction [4-11] of 7 using
termine the stereoselectivity of the cycloaddition step as well as Et2BOMe and NaBH4 at −78 °C gave stable ethylboronate 8 in
for oxidation.
96% yield. Several ethylboronate compounds have been re-
ported [9-11,56-62]. From 8 to 9, no H2O2 treatment was neces-
Oxidation of the 2-isoxazoline 4 with Jones’ reagent gave a sary. Rotary evaporation of 8 with CH3OH at ca. 40 °C easily
complicated mixture, in which the desired carboxylic acid was removed the ethylborane group. Removal of THP in 9 deliv-
not observed (Scheme 2). The stepwise oxidation of the free ered a 1,3,5-trihydroxy compound 10. In another way, 10 could
hydroxy to the carboxy group via intermediary aldehyde was be prepared by treating 8 with PTSA in CH3OH at rt. NMR
then examined. Swern or pyridinium chlorochromate (PCC) ox- spectra of 8–10 exhibited only one set of signals corresponding
idation of 4 also gave a complicated mixture without the desired to the syn-dihydroxy products, indicating an extra high dia-
aldehyde detected. These failed reactions indicated that the stereoselectivity (syn:anti >99:1) during the reduction. To un-
2-isoxazoline moiety could not survive oxidation conditions. ambiguously determine the diastereomeric ratio, the anti-1,3-
Based on this assumption, the corresponding silyl nitronate diol corresponding to 10 was prepared from 7 by RuCl3–PPh3-
from 3-nitropropanal or its acetal were not tried for cycloaddi- catalyzed hydrogenation [63,64]. However, the two diastereo-
tion.
mers had identical proton NMR spectra.
We then set to liberate the β-hydroxy ketone synthon by ring The terminal hydroxy group of 10 was protected with TBS [65-
opening of the isoxazoline 3 (Scheme 3). Raney-Ni-catalyzed 69] and the syn-hydroxy groups subjected to acetonization
hydrogenolysis in the presence of boronic acid had been using PTSA and dimethoxypropane (DMP) to give 12 in 86%
widely utilized to disconnect the N–O bond as well as to total yield [70]. Treatment of 12 with TBAF again liberated the
hydrolyze the resulting imine into a ketone [52]. We applied terminal hydroxy group for further oxidation. RuCl3-catalyzed
Scheme 2: Attempted oxidations of 4.
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Beilstein J. Org. Chem. 2019, 15, 1840–1847.
Scheme 3: Preparations of 16 and related syn-1,3-diol compounds.
Scheme 4: Attempted oxidations of 6'.
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Beilstein J. Org. Chem. 2019, 15, 1840–1847.
oxidation of 13 with NaIO4 yielded the carboxylic acid 14 in results indicated THP, isopropylidene or Ac protection to pri-
86% yield [70], which was reacted with Boc2O to get the tert- mary or secondary hydroxy groups did not well tolerate PTSA-
butyl ester 15 [26,43,71]. The ee of 15 was determined as 74%. catalyzed methanolysis.
The racemic sample of 15 was prepared from racemic diethyl
malate following known methods [26,27]. Finally, K2CO3-cata- Conclusion
lyzed methanolysis gave 16 in 87% yield [26,27]. The absolute In conclusion, we synthesized tert-butyl (3S,5R)-6-hydroxy-3,5-
stereochemistry of 16 was confirmed by crystal structure analy- O-isopropylidene-3,5-dihydroxyhexanoate (16), which is enan-
sis [72] and the specific rotation [28] of 17. Centimeter-long tiomeric to a key intermediate for atorvastatin, from a chiral
prismatic single crystals of 17 were obtained by slow evapora- 2-isoxazoline (3). The β-hydroxy ketone 7 obtained from 3
tion of a petroleum solution.
could be easily converted into several syn-1,3-diol analogs,
demonstrating the usefulness of chiral 2-isoxazolines.
Starting from 9, we tested several reactions in order to selec-
tively protect the internal hydroxy groups (Scheme 5). Though Experimental
not fruitful, these results deserve some comments. The PTSA- 1: To a dry Schlenk tube were added Cu(OTf)2 (144 mg,
catalyzed acetonization of 9 using 2.0 equiv DMP gave the 0.4 mmol), chiral bisoxazoline B (139 mg, 0.52 mmol) and an-
acetonide 18 in a quantitative yield. Treating 18 with a catalyt- hydrous CH2Cl2 (4 mL) under N2. After stirring at room tem-
ic amount of PTSA in methanol gave 10, with the protecting perature for 2 h, a clear solution had formed, which was cooled
groups removed except benzoyl. PTSA-catalyzed acetonization to −50 °C and N-acryloyl-1,3-oxazolidin-2-one (282 mg,
of 10 using 2.0 equiv DMP gave a mixture of two acetonides 19 2 mmol) was added. After stirring for 30 min, a solution of the
and 13, which are separable by silica gel chromatography silyl nitronate (3.0 mmol) in anhydrous CH2Cl2 (6 mL) was
(Scheme 5a). In another trial (Scheme 5b), acylation of the two added. The mixture was stirred for 8 h at −50 °C and monitored
hydroxy groups in 9 yielded 20 in a quantitative yield. PTSA- by TLC. After the reaction was completed, the product was
catalyzed removal of THP in 20 in methanol did occur. How- purified by silica gel chromatography. Yellow oil (923 mg, 95%
ever, concomitant monodeacylation as well as further an acyl- yield); Rf 0.40 (1:1 hexanes/AcOEt); 1H NMR (400 MHz,
transfer reaction also took place, resulting in a mixture. These CDCl3) δ 5.77–5.74 (m, 1H, CH2CHO), 4.53 (s, 1H, OCHO),
Scheme 5: Attempted selective protections of internal 1,3-hydroxy groups: (a) acetonizations of 1,3-diols; (b) removal of co-existing Ac and THP on
hydroxy groups.
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Beilstein J. Org. Chem. 2019, 15, 1840–1847.
ORCID® iDs
4.44 (t, J = 8.0 Hz, 2H, CH2O), 4.03–3.99 (m, 2H, CH2O),
3.79–3.74 (m, 2H, OCH2CH2), 3.47–3.37 (m, 3H, NCH and
NCH2), 2.75–2.66 (m, 1H, CHCH2CH), 2.31–2.27 (m, 1H,
CHCH2CH), 2.17–2.12 (m, 1H, CH2CH2), 1.84–1.79 (m, 2H,
CH2CH2 and CH2CH2CH2), 1.68–1.49 (m, 6H, CH2CH2CH2),
1.24–1.15 (m, 3H, SiCH), 1.07–1.01 (m, 18H, SiCH(CH3)2);
13C NMR (100 MHz, CDCl3) δ 170.8, 153.1, 98.9, 98.9, 77.4,
77.2, 69.9, 69.8, 65.2, 62.8, 62.5, 62.3, 42.6, 35.6, 35.5, 30.7,
30.6, 29.9, 29.8, 25.5, 19.6, 19.5, 18.1, 18.0, 12.2; IR (cm−1):
3544, 2942, 2867, 2725, 2249, 1780, 1704, 1464, 1386, 1275,
1133, 1035, 883, 806, 677; ESIMS (m/z): [M + Na]+ calcd for
C23H42N2O7Si, 509.2659; found, 509.2659.
Peng Jiao - https://orcid.org/0000-0003-4039-8300
Preprint
A non-peer-reviewed version of this article has been previously published
as a preprint doi:10.3762/bxiv.2019.10.v1
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