A Cascade of Prins Reaction and Pinacol-Type Rearrangement: Access to 2,3-Dideoxy-3C-Formyl β-C-Aryl/Alkyl Furanosides and 2-Deoxy-2C-Branched β-C-Aryl Furanoside

Article abstract of DOI:10.1002/ejoc.201801318

2,3-Dideoxy-3C-formyl β-C-aryl/alkyl furanosides were synthesized in a stereoselective manner through a cascade of Prins reaction and pinacol-type rearrangement of an –OTBDPS protected homoallylic alcohol, derived from d-mannitol, and various carbonyl compounds. Furthermore, this method was successfully applied to the synthesis of a fused-bicyclic β-C-aryl furanoside moiety and a 2,3-dideoxy-3C-methyl β-C-aryl furanoside which are found in core structures of bioactive molecules. Further, the strategy was extended to a silyl-Prins reaction for the synthesis of a 2-deoxy-2C-branched β-C-aryl furanoside.

Full text of DOI:10.1002/ejoc.201801318

A Journal of
Accepted Article
Title: A Cascade of Prins Reaction and Pinacol-Type Rearangement:
Access to 2,3-Dideoxy-3C-Formyl β-C-Aryl/Alkyl Furanosides and
2-Deoxy-2C-Branched β-C-Aryl Furanoside
Authors: Sateesh Dubbu, Anirban Bardhan, Ande Chennaiah, and
Yashwant D Vankar
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201801318
Link to VoR: http://dx.doi.org/10.1002/ejoc.201801318
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10.1002/ejoc.201801318
European Journal of Organic Chemistry
1
A Cascade of Prins Reaction and Pinacol-Type Rearangement:
Access to 2,3-Dideoxy-3C-Formyl -C-Aryl/Alkyl Furanosides and
2-Deoxy-2C-Branched -C-Aryl Furanoside
Sateesh Dubbu,[a] Anirban Bardhan,[a]† Ande Chennaiah[a] and Yashwant D. Vankar*[a]
Dedication ((optional))
Abstract: 2,3-Dideoxy-3C-formyl -C-aryl/alkyl furanosides were
synthesized in a stereoselective manner through a cascade of Prins
reaction and pinacol-type rearrangement of an –OTBDPS protected
homoallylic alcohol, derived from D-mannitol, and various carbonyl
compounds. Furthermore, this method was successfully applied to
the synthesis of a fused-bicyclic -C-aryl furanoside moiety and a
2,3-dideoxy-3C-methyl -C-aryl furanoside which are found in core
structures of bioactive molecules. Further, the strategy was
extended to a silyl-Prins reaction for the synthesis of a 2-deoxy-2C-
branched -C-aryl furanoside.
Figure 1: Biologically important tri- and tetrasubstituted C-furanosides.
Introduction
Carbohydrates are essential building blocks for many
cellular processes in living organisms and they exist and act as
physiologically important oligosaccharides in the form of
glycoproteins and glycolipids.[1] Among oligosaccharides, five
membered carbohydrate skeleton (furanose/tetrahydrofuran) is
an important structural motif existing in a wide range of bioactive
polysaccharides.[2] For example, the mycobacterial cell wall is a
highly complex structure and composed of furanose ring of two
lipidated polysaccharides (arabinogalactan complex and
lipoarabinomannan).[2e-h] Among the five membered sugars, C-
furanosides[3] are known to be quite stable and possess
important biological properties. For instance, eribulin 1 (Figure 1)
The Prins reaction is
a versatile strategy for the
construction of a tetrahydropyran/furan ring systems which exist
as a core structure in several natural products.[7] In this direction,
we recently reported a successful utility of the Prins-pinacol-type
rearrangement in carbohydrate chemistry involving C-4-OBn
participation on 1,2-anhydrosugar derived homoallylic alcohols
in the synthesis of
bridged tricyclic ketals.[8] We also
synthesized 2C-branched C-aryl/alkyl glycosides from Perlin-
aldehyde derived substrates through the Prins reaction.[9]
The importance of diversity-oriented synthesis (DOS) in
the development of a small molecular library with potential
biological significance through a diversity-oriented synthesis has
attracted much attention.[10] In continuation of our efforts towards
the synthesis of C-aryl/alkyl glycosides,[8,9,11] more recently we
have reported on the synthesis of a molecular library of 2-deoxy-
3,4-fused C-aryl/alkyl glycosides through the cascade Prins
is an anticancer drug,[4]
which consists of tri- and
tetrasubstituted C-furanoside core motifs. Likewise, bicyclic
pyridinone 2 (Figure 1) is a 2,3-dideoxy-3C-methyl -C-aryl
furanoside and known for the treatment of neurological disorders
such as Alzheimer's disease and Down's syndrome.[5] Further,
synthesis and study of non-natural C-aryl furanosides and their
comparison with C-nucleosides is also an important area of
research to study and for probing them as nucleobases.[3h-3k]
Thus, owing to their fascinating structural features and inherent
biological properties, construction of tri and tetra substituted -C-
aryl/alkyl furanosides[6] in a highly stereoselective manner is a
significantly challenging task in synthetic carbohydrate chemistry.
cyclization of
Depending on the protection of the allylic hydroxyl group of such
D-mannitol derived homoallylic alcohol, 2-deoxy-3,4-fused
a
D-mannitol derived homoallylic alcohol.[12]
a
sugar scaffolds namely isochroman derivatives, bicyclic vinyl
halide derivatives, fluorine substituted tetrahydropyrans and
furan derivatives were procured. The protecting groups used
were benzyl, 1-methylnaphthyl, 2-methylnaphthyl, propargyl,
allyl and substituted allyl ethers. On the other hand, when O-
pivaloyl group was used as a protecting group, it led to a highly
stereoselective
formation
of
2-deoxy--C-aryl/alkyl
glycosides.[13] In view of such protecting group based diverse
reactivity of D-mannitol derived homoallylic alcohol 3, herein, we
report the study of –OTBDPS protecting group on homoallylic
alcohol 3 which led to a stereoselective synthesis of 2,3-
dideoxy-3C-formyl -C-aryl/alkyl furanosides through the Prins-
pinacol rearrangement. Additionally, the homoallylic alcohol 3
was also successfully subjected to the silyl-Prins cyclization for
[a]
†
Prof. Dr. Yashwant. D. Vankar
Sateesh Dubbu, Anirban Bardhan, Ande Chennaiah,
Department of Chemistry, Indian Institute of Technology Kanpur,
Kanpur 208016, India
M.Sc. research project participant (2016).
E-mail: vankar@iitk.ac.in, http://home.iitk.ac.in/~vankar/
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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10.1002/ejoc.201801318
European Journal of Organic Chemistry
2
the construction of a 2-deoxy-2C-branched -C-aryl furanoside
in one step.
solvents at different temperatures. A few protic and Lewis acids
such as trifluoroacetic acid (TFA), InBr3 and Sc(OTf)3 were
screened, but these failed to initiate the reaction (Table 1,
entries-1, 2 and 3). With the use of 0.2 equiv of trimethylsilyl
trifluoromethanesulfonate (TMSOTf) in dichloromethane as a
solvent at 0 °C to room temperature we observed the formation
of 2,3-dideoxy-3C-formyl -C-phenyl furanoside 8a albeit in very
low yield (11%), but formation of C-glycosides 6 and/7 (Table 1,
entry 4) was not observed. No significant improvement was
noticed in the product yield (27%) even after increasing the
catalyst loading to 0.5 equiv of TMSOTf (Table 1, entry 5).
However, to our delight we observed the formation of 8a in 58%
o
yield with 0.5 equiv of BF3•OEt2 at 0 C (Table 1, entry 6). The
o
best results were obtained by using 1.0 equiv BF3•OEt2 at 0 C,
2,3-dideoxy-3C-formyl -C-phenyl furanoside 8a in 89% yield
(Table 1, entry 7). Among the solvents that were used including
acetonitrile, toluene and benzene (Table 1, entries-8, 9 and 10)
the best results observed were with dichloromethane.
Scheme 1. Retrosynthesis of 2,3-dideoxy-3C-formyl -C-aryl/alkyl furanosides
and 2-deoxy-2C-branched -C-aryl furanoside.
Table 1. Optimization of reaction conditions
Results and Discussion
As described above, when the protecting group on the allylic
alcohol part of the D-mannitol derived homoallylic alcohol 3 was
benzyl or a related ether, it led to products other than the
expected C-glycosides 6 and/7 via π-participation. On the other
hand, with
a non-participating –O-pivaloyl protection, C-
glycosides 6 were formed with high stereoselectivity. In view of
these results, we decided to protect the –OH group as
–OTBDPS ether in anticipation of forming products similar to 6
and/7 as it would not involve π participation. Alternatively, we
also expected the Prins-pinacol type rearrangement to occur
with a C-C bond migration once the initial oxocarbenium ion was
formed in a typical Prins reaction (vide infra). These were based
on our recent experience,[8] and also along a somewhat similar
report by Overman et al.[14] It was expected to lead to 2,3-
dideoxy-3C-formyl -C-phenyl furanoside 8a (Table 1) in the
reaction of 3 with benzaldehyde. The required starting material 5
was prepared from 4, by a known strategy as shown in Scheme
2.[15] Thus, regioselective protection of the primary alcohol 4 was
carried out using pivaloyl chloride and pyridine in the presence
of a catalytic amount 4-dimethylaminopyridine (DMAP) to form
–OTBDPS protected homoallylic alcohol 5 in 83% yield (Scheme
2).
a. Yield refers to pure product after column chromatography. NR
reaction.
= no
The scope of the reaction was further evaluated by using
various aldehydes with diverse substitution patterns. In most
cases, the products were obtained in excellent yields and high
selectivity. This method is compatible with a wide range of
functional groups such as nitro, aldehyde, cyano and halides
(Scheme 3). The substituents present on the aromatic ring were
found to have some effects on the conversion.
Scheme 2. Preparation of starting material 5.
We commenced our study by investigating the reactivity of
5 with benzaldehyde using different acid catalysts in various
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10.1002/ejoc.201801318
European Journal of Organic Chemistry
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Scheme 3. Synthesis of 2,3-dideoxy-3C-formyl -C-aryl/alkyl furanosides 8a-8s.
Aromatic aldehydes bearing an electron withdrawing substituent
(Scheme 3, 8c, 8g,8h and 8i) on an aromatic ring gave the
corresponding products in relatively lower yield than with halide
(8e, 8f and 8j-8k), and also with alkyl substituted aryl aldehydes
(8b and 8d). Furthermore, the reaction of –OTBDPS protected
homoallylic alcohol 5 with the p-phthalaldehyde selectively gave
product 8i in 72% yield. This reaction is also quite successful
with cyclohexanone leading to the spiro compound 8q in 73%
yield. Further, we could also procure two novel C-disaccharides
8r and 8s by applying the current protocol.
in Scheme 4. It is presumed that after initial formation of the
Prins-type oxocarbenium ion A it can either undergo [3,3]-
sigmatropic rearrangement to form B, or simply a π-cation
cyclization to form C. Both of these intermediates will then
undergo pinacol-type rearrangement via the transition state D
involving the migration of C-C bond, followed by cleavage of the
–O–SiPh2tBu bond resulting into ring contraction to form 2,3-
dideoxy-3C-formyl -C-aryl furanosides (8a-8s). Alternatively,
the intermediate B may directly give the products 8a-8s,as
shown.
A plausible mechanism to account for the formation of
such 2,3-dideoxy-3C-formyl -C-aryl/alkyl furanosides is shown
The structure of 8a was confirmed by spectral studies and
the stereochemistry of the newly generated stereocenters was
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10.1002/ejoc.201801318
European Journal of Organic Chemistry
4
also X-ray crystallography (CCDC:1583906).[16] It was then
protected as acetate 10 by using Ac2O/Et3N (Scheme 5) whose
solution-state structure was established by NMR experiments
including COSY, NOE and HETCOR.[16] It is worth mentioning
that the molecule 10, having fused-bicyclic -C-aryl furanoside
moiety, is in structural resemblance with the core structure of
(+)-commiphorin, which shows antibacterial activity.[17]
Scheme 5. Synthesis of a fused-bicyclic -C-aryl furanoside 10.
Formation of fused-bicyclic -C-aryl furanoside 9, can be
explained as shown in Scheme 6. Compound 8a may undergo
a base catalyzed equilibration with enolate X upon proton
abstraction from “” carbon of the aldehyde. This intermediate X
could have another equilibration with Y via inversion of the
stereochemistry at C3 position, perhaps to some extent since Y
is sterically more hindered than 8a. Subsequently, basic
hydrolysis of pivaloyl ester in Y with NaOMe in MeOH followed
by cyclization could lead to 9.
Scheme 4. Mechanism for the formation of 2,3-dideoxy-3C-formyl -C-aryl
furanosides 8a-8s.
established based on COSY followed by NOE studies.[16] Thus,
NOE studies of compound 8a revealed that (Figure 2),
irradiation of the H-4 proton at
 4.56 resulted in an
enhancement of the H-1 proton at  4.91–4.90. Also, irradiation
of the H-1 proton at 4.91–4.90 resulted in an enhancement of
the H-4 proton at
 4.57–4.56 and did not show the
enhancement of the H-3 proton. It indicates that H-1 proton is in
cis orientation to H-4 proton but trans to H-3 proton.
PivO
PivO
H
H 4
O
O
1
4
R'
3
R'
OHC
1
H
H
H
3
trans
OHC
cis
R' =
8a
Figure 2. NOE of compound 8a.
Scheme 6. A plausible mechanism for the formation of fused-bicyclic -C-aryl
furanoside 9.
Apparently, the presence of an aldehyde and –O–pivaloyl
group in the 2,3-dideoxy-3C-formyl -C-aryl/alkyl furanoside
skeleton (Scheme 3, 8a-8s), makes it a useful synthetic
precursor for further manipulation. Hence, to get free hydroxyl
compound of 8a, we subjected compound 8a to hydrolysis with
NaOMe in MeOH (Scheme 5). However, surprisingly, we
observed the formation of a fused-bicyclic -C-aryl furanoside 9
with inversion of stereocenter at C-3 position (Scheme 5). The
structure of compound 9 was confirmed by spectral studies, and
2,3-Dideoxy C-furanosides with a methyl group at C-3
position are important scaffolds and are present in several
natural products as a core motifs such as mandelalide A,[18]
gymnodimine,[19] bicyclic pyridinone[5] etc. We therefore thought
of synthesizing a core structure of 2,3-dideoxy-3C-methyl -C-
aryl furanoside 13 (bicyclic pyridinone) by using this
methodology. Toward this, 2,3-dideoxy-3C-formyl -C-aryl
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10.1002/ejoc.201801318
European Journal of Organic Chemistry
5
furanoside 8c was first reduced with NaBH4 to the corresponding
primary alcohol 11 which was then converted to the final
molecule 13 via Appel reaction followed by LiAlH4 reduction of
the iodide 12 (Scheme 7). Thus, the present route provides an
easy alternative route to obtain 2,3-dideoxy C-3 methyl C-
furanosides.
A plausible reaction pathway for the silyl-Prins cyclization
is shown in Scheme 10. The reaction is likely to proceed through
an oxocarbenium ion I formed upon reaction of the homologated
allylsilane homoallylic alcohol 15 with p-tolualdehyde. In this
reaction, BF3•OEt2 activates the aldehyde thus facilitating the
formation of an oxocarbenium ion I, which is then attacked by an
Scheme 7. Synthesis of core moiety of bicyclic pyridinone 13.
Having demonstrated the use of –OTBDPS protected
homoallylic alcohol 5, we turned our attention to extend the
chain of the homoallylic alcohol of type 3 to form an allylsilane
15 and then check its feasibility in silyl-Prins cyclization. The
requisite precursor 15 was prepared from –OBn protected
homoallylic alcohol 14, obtained from D-mannitol,[12] upon cross
metathesis reaction with allylsilane in presence of Grubbs 2nd
generation catalyst (5 mol %) in CH2Cl2 for 15 h at reflux
(Scheme 8).
Scheme 9. Synthesis of 2-deoxy-2C-branched -C-aryl furanoside 17a and
17b.
internal olefin to generate -silyl carbocation III, via the
conformation II. Subsequently, the intermediate III hydrolytically
decomposes to give corresponding products 17a. On the other
hand the formation of minor diastereomer can be explained via
the confomation IV which leads product 17b via -silyl
carbocation V followed by silyl group elimination with the help of
a nucleophile present in reaction medium.
Scheme 8. Synthesis of homologated allylsilane homoallylic alcohol 15.
Treatment of the homologated allylsilane homoallylic
o
alcohol 15 with p-tolualdehyde using 1.0 equiv BF3•OEt2 at 0 C
in dichloromethane (Table 1, entry 7) as a solvent gave the
corresponding 2-deoxy-2C-branched -C-aryl furanoside 16 in
good yield (84%) as an inseparable diastereomeric mixture (:
= 0.8:1 ratio) (Scheme 9). In order to separate the stereoisomers,
compound 16 was subjected to deprotection of the –OPiv group
using NaOMe/MeOH to give diastereomers 17a and 17b which
were separated by column chromatography in 43% and 35%
yield respectively. The structures of 17a and 17b were
confirmed based on spectral studies and the stereochemistry of
the newly generated stereocenters was established based on
COSY followed by NOE studies.[16] Further work to explore the
scope of this silyl-Prins reaction is underway and will be reported
in due course of time.
Scheme 10. Mechanism for the formation of 2-deoxy-2C-branched -C-aryl
furanoside 16.
The stereochemistry of newly generated stereocenters
was proved by spectral means. Thus, NOE studies[16] of
compound 17a revealed that (Figure 3), irradiation of the H-4
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10.1002/ejoc.201801318
European Journal of Organic Chemistry
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(doublet of triplet). IR spectra were recorded on Bruker FT/IR Vector 22
spectrometer and are expressed in cm-1. Optical rotations were
measured using a polarimeter (AUTOPOL II) at 28 °C. Mass spectra
were obtained from high resolution ESI mass spectrometer using QTOF
analyser.
proton at  4.07 resulted in an enhancement of the H-1 proton at
 5.25 and H-2 proton at  3.16. It indicates that H-4 proton is cis
to H-1 and H-2 protons. In the NOE studies of compound 17b
(Figure 3), irradiation of the H-4 proton at  4.19 resulted in an
enhancement of the H-1 proton at  4.87 and did not result in the
enhancement of the H-2 proton. Further, irradiation of the H-2
proton at  2.71 and did not result in the enhancement of the H-4
proton. It indicates that H-4 proton is in cis relationship with H-1
proton, but in trans relationship with H-2 proton.
General experimental procedures:
(2R,3S)-3-((Tert-butyldiphenylsilyl)oxy)-2-hydroxypent-4-en-1-yl
pivalate (5):
Compound
4 was prepared by following a
literature proecedure.15
Compound 4 (500 mg, 1.40 mmol) was dissolved in CH2Cl2 (8 mL) and
cooled to 0 °C. Pivaloyl chloride (0.17 mL, 1.40 mmol), pyridine (0.13 mL,
1.68 mmol) and DMAP (17 mg, 0.14 mmol) were added to this mixture
and allowed to stir at room temperature for 8 h. After completion of the
reaction (TLC monitoring), it was quenched with water (5 mL) and then
extracted with CH2Cl2 (3 x 10 mL). The combined organic extracts were
washed with water (2 x 15 mL), brine (1 x 15 mL) solution, dried over
Na2SO4 and concentrated in vacuo. Column chromatography of the crude
reaction mixture afforded 5 as a colorless thick liquid. Yield = 568 mg,
91%; Rf = 0.6 (9/1 hexane/EtOAc);
= +18.02° (c = 0.51, CH2Cl2); IR
(ṽmax/cm−1) 3514, 2961, 2859, 1732, 1428; 1H NMR (400 MHz, CDCl3) δ
7.69–7.63 (m, 4H), 7.46–7.34 (m, 6H), 5.87–5.78 (m, 1H), 5.09–5.07 (m,
1H), 4.97–4.92 (m, 1H), 4.20 (dd, J = 7.4, 3.9 Hz, 1H), 4.09–4.04 (m, 2H),
3.81 (dd, J = 10.0, 5.8 Hz, 1H), 2.34 (br s, 1H), 1.12 (s, 9H), 1.08 (s, 9H);
13C NMR (100 MHz, CDCl3) δ 178.55, 136.10, 135.99, 135.54, 133.47,
133.42, 130.08, 129.92, 127.86, 127.64, 118.53, 76.30, 72.90, 64.64,
38.84, 27.24, 27.16, 19.50; HRMS calcd for C26H40NO4Si [M + NH4]+
458.2727, found 458.2720.
Figure 3. NOE of compound 17a and 17b.
Conclusions
In summary, we have developed a facile method for the
stereoselective synthesis of 2,3-dideoxy-3C-formyl -C-aryl/alkyl
furanosides through Prins-pinacol rearrangement of –OTBDPS
protected homoallylic alcohol derived from D-mannitol. This
cascade reaction is compatible with a variety of carbonyl
compounds to give the corresponding 2,3-dideoxy-3C-formyl -
C-aryl/alkyl furanosides in good to excellent yields. Furthermore,
this method was successfully applied to the synthesis of a fused-
bicyclic -C-aryl furanoside moiety and a 2,3-dideoxy-3C-methyl
-C-aryl furanoside which are found in core structures of
bioactive molecules. Additionally, the strategy was extended to a
silyl-Prins reaction for the synthesis of a 2-deoxy-2C-branched
-C-aryl furanoside whose further scope is being investigated
and will form a part of future publication.
General procedure for the synthesis of 2,3-dideoxy-3C-formyl -C-
aryl/alkyl
furanosides
and
2-deoxy-2C-branched
-C-aryl
furanoside:
To a stirred solution of homoallylic alcohol 5/15 (200 mg, 0.45 mmol, 1.0
equiv/200 mg, 0.57 mmol, 1.0 equiv) and aldehyde (0.54 mmol, 1.1
equiv/) in dichloromethane (3 mL) was added BF3•OEt2 (58 µL, 0.45
mmol, 1.0 equiv) at 0 ºC. The resulting reaction mixture was stirred at
same temperature until the starting material was completely consumed
(TLC monitoring) (specified in Scheme 3). The reaction mixture was
quenched by adding a saturated aqueous NaHCO3 (3 mL) solution and
extracted with dichloromethane (3
x 5 mL). The combined organic
extracts were washed with water (2 x 5 mL), brine (1 x 5 mL) solution,
dried over Na2SO4 and concentrated in vacuo. Column chromatography
of the crude reaction mixture afforded C-furanosides (Scheme 3 and
Scheme 9).
Following the general procedure for the for the synthesis of 2,3-
dideoxy-3C-formyl
furanosides, compounds 8a-8s and 16 were prepared:
and
2-deoxy-2C-branched
-C-aryl/alkyl
Experimental Section
General procedure:
((2S,3S,5R)-3-Formyl-5-phenyltetrahydrofuran-2-yl)methyl pivalate
(8a):
All the dry solvents were prepared according to the standard procedures.
All other reagents were used as received from either Aldrich,
Spectrochem Pvt. Ltd. (Mumbai), Sd fine-chem Ltd. (Mumbai) and
Lancaster chemical companies. Melting points were determined on a
micro hot-stage (Yanako MP-S3). The visualization of spots on TLC
plates was effected by exposure to iodine or spraying with 10% H2SO4
and charring. Column chromatography was performed over silica gel
(100200 Mesh) using hexane and ethyl acetate as eluents. 1H and 13C
were recorded on JEOL ECX-500 (500 and 125 MHz) spectrometer or
JEOL LA-400 (400 and 100 MHz) spectrometer in solution of CDCl3 using
tetramethylsilane as the internal standard. Coupling constants are
reported and expressed in Hz; splitting patterns are designated as br
(broad), s (singlet), d (doublet), dd (double doublet), m (multiplet), dt
Colorless liquid; Yield = 117 mg, 89%; Rf = 0.5 (8/2 hexane/EtOAc);
= +27.14° (c = 0.341, CH2Cl2); IR (ṽmax/cm−1) 2971, 2872, 1728, 1282,
1158; 1H NMR (500 MHz, CDCl3) δ 9.82 (s, 1H, –CHO), 7.36–7.26 (m,
5H, ArH), 4.92 (dd, J = 9.0, 6.4 Hz, 1H, H-1), 4.57 (dd, J = 9.7, 4.8 Hz,
1H, H-4), 4.32 (m, J = 6.7 Hz, 2H, H-5,5’), 3.14–3.10 (m, 1H, H-3), 2.67–
2.66 (m, 1H, H-2), 2.12–2.06 (m, 1H, H-2’), 1.22 (s, 9H, –C(CH3)3); 13C
NMR (125 MHz, CDCl3) δ 199.93, 178.38, 141.12, 128.63, 127.99,
125.77, 80.95, 76.67, 65.47, 54.23, 39.02, 35.59, 27.37; HRMS calcd for
C
17H22O4 [M]+ 290.1518, found 290.1516.
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10.1002/ejoc.201801318
European Journal of Organic Chemistry
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((2S,3S,5R)-3-Formyl-5-(p-tolyl)tetrahydrofuran-2-yl)methyl pivalate
((2S,3S,5R)-3-Formyl-5-(4-nitrophenyl)tetrahydrofuran-2-yl)methyl
(8b):
pivalate (8g):
Pale yellow liquid; Yield = 125 mg, 90%; Rf = 0.5 (8/2 hexane/EtOAc);
= -12.63° (c = 0.71, CH2Cl2); IR (ṽmax/cm−1) 2973, 2873, 1730, 1283,
1159; 1H NMR (500 MHz, CDCl3) δ 9.81 (s, 1H), 7.26–7.15 (m, 4H), 4.88
(dd, J = 9.1, 6.3 Hz, 1H), 4.56 (dd, J = 9.8, 4.6 Hz, 1H), 4.35–4.30 (m,
2H), 3.13–3.11 (m, 1H), 2.65–2.64 (m, 1H), 2.34 (s, 3H), 2.08 (dt, J =
12.9, 9.5 Hz, 1H), 1.23 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 200.05,
178.40, 138.01, 137.73, 129.28, 129.13, 125.77, 80.90, 76.51, 65.49,
54.26, 39.01, 35.57, 27.36, 21.26; HRMS calcd for C18H24NaO4 [M + Na]+
327.1572, found 327.1570.
Pale yellow liquid; Yield = 112 mg, 73%; Rf = 0.5 (7/3 hexane/EtOAc);
= +38.18° (c = 0.72, CH2Cl2); IR (ṽmax/cm−1) 2973, 2872, 1727, 1522,
1347; 1H NMR (500 MHz, CDCl3) δ 9.83 (d, J = 1.1 Hz, 1H), 8.21 (d, J =
8.8 Hz, 2H), 7.52 (d, J = 8.6 Hz, 2H), 5.00 (dd, J = 9.2, 6.5 Hz, 1H), 4.65–
4.62 (m, 1H), 4.35 (dd, J = 4.3, 2.4 Hz, 2H), 3.18–3.15 (m, 1H), 2.81–
2.76 (m, 1H), 2.05–1.99 (m, 1H), 1.22 (s, 9H); 13C NMR (125 MHz,
CDCl3) δ 199.24, 178.30, 148.68, 147.65, 126.37, 123.92, 79.83, 77.08,
65.29, 53.87, 39.03, 35.38, 27.36; HRMS calcd for C17H22NO6 [M + H]+
336.1447, found 336.1443.
((2S,3S,5R)-3-Formyl-5-(4-(trifluoromethyl)phenyl)tetrahydrofuran-2-
((2S,3S,5R)-5-(4-Cyanophenyl)-3-formyltetrahydrofuran-2-yl)methyl
yl)methyl pivalate (8c):
pivalate (8h):
Pale yellow liquid; Yield = 134 mg, 82%; Rf = 0.5 (8/2 hexane/EtOAc);
= +52.18° (c = 1.22, CH2Cl2); IR (ṽmax/cm−1) 2975, 1729, 1326, 1163,
1067; 1H NMR (400 MHz, CDCl3) δ 9.83 (d, J = 1.3 Hz, 1H), 7.61 (d, J =
8.2 Hz, 2H), 7.46 (d, J = 8.2 Hz, 2H), 4.97 (dd, J = 9.1, 6.5 Hz, 1H), 4.61
(dd, J = 9.8, 4.5 Hz, 1H), 4.34–4.33 (m, 2H), 3.17–3.12 (m, 1H), 2.77–
2.71 (m, 1H), 2.04 (dt, J = 12.8, 9.4 Hz, 1H), 1.22 (s, 9H); 13C NMR (125
MHz, CDCl3) δ 199.56, 178.37, 145.30, 125.94, 125.62, 125.59, 80.17,
76.87, 65.36, 53.98, 39.03, 35.47, 27.35; HRMS calcd for C18H22F3O4 [M
+ H]+ 359.1470, found 359.1470.
Pale yellow liquid; Yield = 114 mg, 79%; Rf = 0.5 (8/2 hexane/EtOAc);
= -21.42° (c = 0.32, CH2Cl2); IR (ṽmax/cm−1) 2964, 2874, 2229, 1730,
1282; 1H NMR (400 MHz, CDCl3) δ 9.82 (d, J = 1.3 Hz, 1H), 7.64 (d, J =
8.4 Hz, 2H), 7.46 (d, J = 8.1 Hz, 2H), 4.96 (dd, J = 9.2, 6.4 Hz, 1H), 4.62
(dd, J = 9.7, 4.4 Hz, 1H), 4.34–4.4.33 (m, 2H), 3.17–3.12 (m, 1H), 2.78–
2.72 (m, 1H), 2.05–1.97 (m, 1H), 1.21 (s, 9H); 13C NMR (100 MHz,
CDCl3) δ 199.33, 176.39, 146.77, 132.51, 132.50, 126.32, 126.29, 80.10,
64.84, 53.88, 45.46, 39.04, 35.34, 27.35; HRMS calcd for C18H22NO4 [M
+ H]+ 316.1549, found 316.1543.
((2S,3S,5R)-3-Formyl-5-(4-isopropylphenyl)tetrahydrofuran-2-
((2S,3S,5R)-3-Formyl-5-(4-formylphenyl)tetrahydrofuran-2-yl)methyl
yl)methyl pivalate (8d):
pivalate (8i):
Pale yellow liquid; Yield = 137 mg, 90%; Rf = 0.5 (8/2 hexane/EtOAc);
= -13.07° (c = 0.24, CH2Cl2); IR (ṽmax/cm−1) 2961, 2872, 1730, 1480,
1283; 1H NMR (500 MHz, CDCl3) δ 9.81 (d, J = 1.6 Hz, 1H), 7.27 (d, J =
8.2 Hz, 2H), 7.20 (d, J = 8.2 Hz, 2H), 4.88 (dd, J = 9.2, 6.4 Hz, 1H), 4.56
(dd, J = 9.9, 4.8 Hz, 1H), 4.32–4.31 (m, 2H), 3.14–3.10 (m, 1H), 2.92–
2.87 (m, 1H), 2.67–2.62 (m, 1H), 2.11 (dt, J = 12.9, 9.5 Hz, 1H), 1.23 (s,
9H), 1.23 (s, 6H); 13C NMR (125 MHz, CDCl3) δ 200.05, 178.37, 148.77,
138.30, 126.67, 125.90, 80.93, 76.52, 65.49, 54.29, 39.00, 35.42, 33.97,
27.36, 24.12, 24.09; HRMS calcd for C20H29O4 [M + H]+ 333.2066, found
333.2069.
Pale yellow liquid; Yield = 105 mg, 72%; Rf = 0.3 (8/2 hexane/EtOAc);
= +32.07° (c = 0.62, CH2Cl2); IR (ṽmax/cm−1) 2923, 2853, 1728, 1701,
1609; 1H NMR (500 MHz, CDCl3) δ 10.01 (s, 1H), 9.83 (d, J = 1.4 Hz,
1H), 7.87 (d, J = 8.1 Hz, 2H), 7.52 (d, J = 8.1 Hz, 2H), 4.99 (dd, J = 9.1,
6.5 Hz, 1H), 4.62 (dd, J = 9.7, 4.5 Hz, 1H), 4.38–4.32 (m, 2H), 3.17–3.13
(m, 1H), 2.78–2.73 (m, 1H), 2.09–2.02 (m, 1H), 1.22 (s, 9H); 13C NMR
(125 MHz, CDCl3) δ 199.48, 191.97, 178.35, 148.19, 136.09, 130.15,
126.17, 80.31, 76.96, 65.35, 53.97, 39.03, 35.44, 27.37; HRMS calcd for
C
18H23O5 [M + H]+ 319.1545, found 319.1543.
((2S,3S,5R)-5-(3-Bromophenyl)-3-formyltetrahydrofuran-2-yl)methyl
((2S,3S,5R)-5-(4-Bromophenyl)-3-formyltetrahydrofuran-2-yl)methyl
pivalate (8j):
pivalate (8e):
Pale yellow liquid; Yield = 152 mg, 90%; Rf = 0.5 (8/2 hexane/EtOAc);
= +17.27° (c = 1.75, CH2Cl2); IR (ṽmax/cm−1) 2972, 2873, 1729, 1480,
1093; 1H NMR (400 MHz, CDCl3) δ 9.81 (d, J = 1.4 Hz, 1H), 7.52 (s, 1H),
7.41 (dt, J = 7.5, 1.7 Hz, 1H), 7.26–7.18 (m, 2H), 4.87 (dd, J = 9.2, 6.4 Hz,
1H), 4.58 (dd, J = 9.7, 4.4 Hz, 1H), 4.36–4.29 (m, 2H), 3.15–3.10 (m, 1H),
2.71–2.26 (m, 1H), 2.04 (dt, J = 12.9, 9.5 Hz, 1H), 1.23 (s, 9H); 13C NMR
(100 MHz, CDCl3) δ 199.58, 178.34, 143.61, 131.00, 130.17, 128.71,
124.38, 122.83, 80.07, 76.79, 65.35, 53.98, 39.01, 35.54, 27.37; HRMS
calcd for C17H21BrNaO4 [M + Na]+ 391.0521, found 391.0519.
Pale yellow liquid; Yield = 154 mg, 92%; Rf = 0.5 (8/2 hexane/EtOAc);
= -27.07° (c = 0.57, CH2Cl2); IR (ṽmax/cm−1) 2972, 2933, 1730, 1283,
1158; 1H NMR (400 MHz, CDCl3) δ 9.81 (d, J = 1.3 Hz, 1H), 7.47 (d, J =
8.4 Hz, 2H), 7.22 (d, J = 8.4 Hz, 2H), 4.86 (dd, J = 9.2, 6.3 Hz, 1H), 4.57
(dd, J = 9.7, 4.6 Hz, 1H), 4.32–4.31 (m, 2H), 3.19–2.98 (m, 1H), 2.70–
2.64 (m, 1H), 2.02 (dt, J = 12.9, 9.5 Hz, 1H), 1.22 (s, 9H); 13C NMR (100
MHz, CDCl3) δ 199.65, 178.34, 140.25, 131.73, 127.43, 121.75, 80.25,
76.74, 65.38, 54.06, 39.02, 35.49, 27.36; HRMS calcd for C17H21BrNaO4
[M + Na]+ 391.0521, found 391.0519.
((2S,3S,5R)-5-(3-Fluorophenyl)-3-formyltetrahydrofuran-2-yl)methyl
((2S,3S,5R)-5-(4-Fluorophenyl)-3-formyltetrahydrofuran-2-yl)methyl
pivalate (8k):
pivalate (8f):
Pale yellow liquid; Yield = 127 mg, 90%; Rf = 0.5 (8/2 hexane/EtOAc);
= +7.23° (c = 0.47, CH2Cl2); IR (ṽmax/cm−1) 2960, 2926, 1731, 1283,
1158; 1H NMR (400 MHz, CDCl3) δ 9.81 (d, J = 1.3 Hz, 1H), 7.33–7.27
(m, 1H), 7.10–7.07 (m, 2H), 6.99–6.94 (m, 1H), 4.91 (dd, J = 9.0, 6.5 Hz,
1H), 4.59 (dd, J = 9.9, 4.5 Hz, 1H), 4.33–4.32 (m, 2H), 3.14–3.12 (m, 1H),
2.69–2.67 (m, 1H), 2.06 (dt, J = 12.9, 9.4 Hz, 1H), 1.22 (s, 9H); 13C NMR
(100 MHz, CDCl3) δ 199.68, 178.40, 130.15, 121.30, 114.71, 112.73,
80.17, 76.91, 65.38, 53.98, 39.02, 35.51, 27.36; HRMS calcd for
Pale yellow liquid; Yield = 128 mg, 91%; Rf = 0.5 (8/2 hexane/EtOAc);
= +42.27° (c = 1.31, CH2Cl2); IR (ṽmax/cm−1) 2973, 1730, 1512, 1226,
1157; 1H NMR (400 MHz, CDCl3) δ 9.81 (d, J = 1.4 Hz, 1H), 7.34–7.26
(m, 2H), 7.06–7.00 (m, 2H), 4.88 (dd, J = 9.2, 6.2 Hz, 1H), 4.57 (dd, J =
9.9, 4.6 Hz, 1H), 4.33–4.31 (m, 2H), 3.14–3.11 (m, 1H), 2.66–2.63 (m,
1H), 2.04 (dt, J = 12.8, 9.5 Hz, 1H), 1.22 (s, 9H); 13C NMR (100 MHz,
CDCl3) δ 199.77, 178.35, 136.83, 127.50, 127.42, 115.60, 115.39, 80.35,
76.65, 65.43, 54.15, 39.02, 35.60, 27.36; HRMS calcd for C17H21FNaO4
[M + Na]+ 331.1322, found 331.1319.
C
17H21FNaO4 [M + Na]+ 331.1322, found 331.1319.
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201801318
European Journal of Organic Chemistry
8
((2S,3S,5R)-5-(2,3-Dichlorophenyl)-3-formyltetrahydrofuran-2-
yl)methyl pivalate (8l):
Pale yellow liquid; Yield = 130 mg, 73%; Rf = 0.5 (8/2 hexane/EtOAc);
= +28.11° (c = 0.31, CH2Cl2); IR (ṽmax/cm−1) 2933, 2859, 1732, 1712,
1285; 1H NMR (400 MHz, CDCl3) δ 9.71 (d, J = 2.3 Hz, 1H), 4.44–4.36
(m, 1H), 4.22–4.12 (m, 2H), 3.04–2.97 (m, 1H), 2.08–1.96 (m, 2H), 1.66–
1.24 (m, 8H), 1.20 (s, 9H), 1.19–1.04 (m, 2H); 13C NMR (100 MHz,
CDCl3) δ 200.58, 178.31, 83.95, 75.46, 65.61, 54.74, 38.21, 37.87, 37.34,
27.33, 25.52, 23.74, 23.60; HRMS calcd for C16H26O4 [M]+ 282.1831,
found 282.1829.
Pale yellow liquid; Yield = 134 mg, 82%; Rf = 0.5 (8/2 hexane/EtOAc);
= +14.34° (c = 0.21, CH2Cl2); IR (ṽmax/cm−1) 2971, 1729, 1480, 1282,
1153; 1H NMR (400 MHz, CDCl3) δ 9.82 (d, J = 1.6 Hz, 1H), 7.54–7.20
(m, 3H), 5.25–5.21 (m, 1H), 4.61 (dt, J = 6.2, 4.2 Hz, 1H), 4.42–4.32 (m,
2H), 3.12–3.07 (m, 1H), 2.98–2.92 (m, 1H), 1.99–1.91 (m, 1H), 1.22 (s,
9H); 13C NMR (100 MHz, CDCl3) δ 199.49, 178.36, 141.88, 133.18,
129.54, 127.66, 124.50, 78.12, 65.08, 53.66, 39.04, 33.99, 27.37; HRMS
calcd for C17H21Cl2O4 [M + H]+ 359.0817, found 359.0810.
((2S,3S,5R)-3-Formyl-5-(((2S,3S,4R,5R,6R)-3,4,5-trimethoxy-6-
(methoxymethyl)tetrahydro-2H-pyran-2-yl)methyl)tetrahydrofuran-2-
yl)methyl pivalate (8r):
((2S,3S,5R)-5-(3,5-Dichlorophenyl)-3-formyltetrahydrofuran-2-
yl)methyl pivalate (8m):
Pale yellow liquid; Yield = 152 mg, 74%; Rf = 0.5 (5/5 hexane/EtOAc);
= +27.01° (c = 0.47, CH2Cl2); IR (ṽmax/cm−1) 2935, 2829, 1730, 1283,
1101; 1H NMR (400 MHz, CDCl3) δ 9.72 (d, J = 1.8 Hz, 1H), 4.37 (dd, J =
10.6, 4.9 Hz, 1H), 4.18–4.13 (m, 3H), 4.08–4.01 (m, 1H), 3.60 (s, 3H),
3.55–3.53 (m, 1H), 3.52 (s, 3H), 3.49–3.44 (m, 1H), 3.43 (s, 3H), 3.38 (s,
3H), 3.34–3.16 (m, 4H), 2.99–2.94 (m, 1H), 2.45–2.39 (m, 1H), 2.08–2.00
(m, 1H), 1.87 (dt, J = 12.7, 9.3 Hz, 1H), 1.76–1.70 (m, 1H), 1.21 (s, 9H);
13C NMR (125 MHz, CDCl3) δ 200.11, 178.24, 83.86, 81.41, 79.70, 77.26,
76.27, 71.43, 71.40, 65.51, 60.67, 60.45, 59.28, 58.77, 54.05, 38.93,
32.26, 30.52, 27.31; HRMS calcd for C22H39O9 [M + H]+ 447.2594, found
447.2591.
Pale yellow liquid; Yield = 140 mg, 86%; Rf = 0.5 (8/2 hexane/EtOAc);
= +21.45° (c = 0.51, CH2Cl2); IR (ṽmax/cm−1) 2971, 2934, 1731, 1570,
1103; 1H NMR (400 MHz, CDCl3) δ 9.81 (d, J = 1.1 Hz, 1H), 7.30–7.22
(m, 3H), 4.85 (dd, J = 9.1, 6.4 Hz, 1H), 4.60 (dd, J = 9.3, 4.2 Hz, 1H),
4.37–4.28 (m, 2H), 3.17–3.12 (m, 1H), 2.73–2.68 (m, 1H), 2.02 (dt, J =
12.9, 9.4 Hz, 1H), 1.23 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 199.34,
178.37, 144.87, 135.27, 128.00, 124.17, 79.52, 76.90, 65.28, 53.77,
39.02, 35.45, 27.37; HRMS calcd for
found 359.0813.
C
17H21Cl2O4 [M + H]+ 359.0817,
((2S,3S,5R)-5-(((2S,3R,4R,5R)-3,4-Dimethoxy-5-
(methoxymethyl)tetrahydrofuran-2-yl)methyl)-3-
formyltetrahydrofuran-2-yl)methyl pivalate (8s):
((2S,3S,5R)-3-Formyl-5-(naphthalen-2-yl)tetrahydrofuran-2-yl)methyl
pivalate (8n):
Pale yellow liquid; Yield = 113 mg, 73%; Rf = 0.5 (8/2 hexane/EtOAc);
= +30.74° (c = 1.02, CH2Cl2); IR (ṽmax/cm−1) 2972, 2872, 1728,1480,
1282; 1H NMR (400 MHz, CDCl3) δ 9.85 (d, J = 1.5 Hz, 1H), 7.85–7.79
(m, 4H), 7.50–7.43 (m, 3H), 5.09 (dd, J = 9.1, 6.3 Hz, 1H), 4.64 (dd, J =
10.0, 4.6 Hz, 1H), 4.39–4.37 (m, 2H), 3.18–3.15 (m, 1H), 2.74–2.73 (m,
1H), 2.17 (dt, J = 12.9, 9.5 Hz, 1H), 1.24 (s, 9H); 13C NMR (100 MHz,
Colorless liquid; Yield = 133 mg, 72%; Rf = 0.7 (5/5 hexane/EtOAc);
= +12.01° (c = 0.19, CH2Cl2); IR (ṽmax/cm−1) 2933, 2827, 1729, 1284,
1160; 1H NMR (500 MHz, CDCl3) δ 9.71 (s, 1H), 4.36 (dd, J = 10.5, 5.0
Hz, 1H), 4.19–4.13 (m, 2H), 4.07–4.00 (m, 2H), 3.86 (td, J = 5.9, 3.7 Hz,
1H), 3.59–3.46 (m, 4H), 3.39 (s, 6H), 3.37 (s, 3H), 2.96–2.92 (m, 1H),
2.42–2.36 (m, 1H), 1.95–1.77 (m, 3H), 1.21 (s, 9H); 13C NMR (125 MHz,
CDCl3) δ 200.19, 178.22, 86.00, 85.34, 82.17, 78.78, 77.46, 76.24, 73.52,
65.49, 59.33, 57.38, 57.19, 54.18, 38.90, 34.73, 33.25, 27.29; HRMS
calcd for C20H35O8 [M + H]+ 403.2332, found 403.2330.
CDCl3)
δ 199.90, 178.41, 138.52, 133.37, 133.22, 128.51, 128.07,
127.85, 126.41, 126.13, 124.57, 123.73, 81.09, 65.52, 54.29, 39.05,
35.61, 27.40; HRMS calcd for C21H24O4 [M]+ 340.1675, found 340.1670.
((2S,3S,5S)-3-Formyl-5-propyltetrahydrofuran-2-yl)methyl
(8o):
pivalate
(2R,3aR,4R,6aS)-2-Phenylhexahydrofuro[3,4-b]furan-4-ol (9):
Compound 8a (300 mg, 1.45 mmol) was dissolved in dry MeOH (3 mL)
and cooled to 0 °C. To this reaction mixture was added a catalytic
amount of NaOMe (8 mg, 0.45 mmol) and then the mixture was stirred
Pale yellow liquid; Yield = 85 mg, 73%; Rf = 0.7 (8/2 hexane/EtOAc);
= +51.11° (c = 1.27, CH2Cl2); IR (ṽmax/cm−1) 2961, 2933, 1732, 1514,
1481; 1H NMR (400 MHz, CDCl3) δ 9.73 (d, J = 1.9 Hz, 1H), 4.35 (dd, J =
10.6, 5.0 Hz, 1H), 4.21–4.14 (m, 2H), 3.93–3.86 (m, 1H), 2.98–2.93 (m,
1H), 2.36–2.30 (m, 1H), 1.82–1.74 (m, 1H), 1.62–1.57 (m, 1H), 1.47–1.33
(m, 3H), 1.21 (s, 9H), 0.93 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3) δ 200.42, 178.33, 79.65, 76.14, 65.49, 54.21, 38.96, 37.74, 32.56,
27.32, 19.35, 14.21; HRMS calcd for C14H25O4 [M + H]+ 257.1753, found
257.1758.
for
3 h at room temperature. After completion of reaction (TLC
monitoring), MeOH was evaporated and the residue was diluted with
water (5 mL). It was extracted with EtOAc (3 x 8 mL) and organic layer
was washed with brine (1 x 5 mL). Evaporation of the organic solvent
followed by purification using silica gel column chromatography gave
compound 9 as a white solid; Yield = 116 mg, 77%; M.P. = 127–129 °C;
Rf = 0.5 (7/3 hexane/EtOAc);
= +8.01° (c = 0.51, CH2Cl2); IR
(ṽmax/cm−1) 3414, 2934, 1454, 1096, 1026; 1H NMR (400 MHz, CDCl3) δ
7.38–7.25 (m, 5H), 5.36 (s, 1H), 4.81–4.74 (m, 2H), 4.18–4.12 (m, 2H),
3.02–2.96 (m, 2H), 2.58–2.51 (m, 1H), 1.66–1.58 (m, 1H); 13C NMR (100
MHz, CDCl3) δ 140.50, 130.55, 128.52, 126.15, 103.66, 83.32, 82.99,
72.44, 52.20, 39.76; HRMS calcd for
found 229.0838.
((2S,3S,5R)-5-Cyclohexyl-3-formyltetrahydrofuran-2-yl)methyl
pivalate (8p):
Colorless liquid; Yield = 99 mg, 73%; Rf = 0.5 (8/2 hexane/EtOAc);
=
C
12H14NaO3 [M + Na]+ 229.0841,
+4.91° (c = 0.23, CH2Cl2); IR (ṽmax/cm−1) 2926, 2853, 1730, 1283, 1160;
1H NMR (400 MHz, CDCl3) δ 9.72 (d, J = 1.8 Hz, 1H), 4.34 (dd, J = 10.2,
5.4 Hz, 1H), 4.21–4.11 (m, 2H), 3.63–3.58 (m, 1H), 2.93–2.88 (m, 1H),
2.29–2.23 (m, 1H), 1.91–1.11 (m, 6H), 1.43–1.34 (m, 2H), 1.21 (s, 9H),
1.29–1.13 (m, 2H), 1.05–0.93 (m, 2H); 13C NMR (100 MHz, CDCl3) δ
200.54, 178.34, 84.15, 75.96, 65.43, 54.15, 42.94, 38.97, 30.17, 29.72,
28.94, 27.34, 26.54, 26.07, 25.92; HRMS calcd for C17H29O4 [M + H]+
297.2066, found 297.2064.
(2R,3aR,4S,6aS)-2-Phenylhexahydrofuro[3,4-b]furan-4-yl
acetate
(10):
To a stirred solution of acetal 9 (100 mg, 0.47 mmol) in dry CH2Cl2 (2 mL)
at 0 °C under nitrogen atmosphere was added Et3N (81 L, 0.57 mmol),
followed by addition of acetic anhydride (58 L, 0.57 mmol) and a
catalytic amount of DMAP (6 mg, 0.04 mmol) at same temperature for 15
mim. On completion of the reaction (TLC monitoring), saturated NaHCO3
solution (3 mL) was added and reaction mixture was stirred for 10 min.
((2S,3S)-3-Formyl-1-oxaspiro[4.5]decan-2-yl)methyl pivalate (8q):
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10.1002/ejoc.201801318
European Journal of Organic Chemistry
9
Extraction was done with CH2Cl2 (3 x 8 mL), and combined organic
extracts were washed with water (1 x 10 mL) and brine solution (1 x 10
mL) and then dried over Na2SO4. Concentration in vacuo gave crude
residue which was purified by column chromatography to obtain 10 as a
pale yellow liquid; Yield = 109 mg, 90%; Rf = 0.5 (5/5 hexane/EtOAc);
= +27.01° (c = 0.47, CH2Cl2); IR (ṽmax/cm−1) 2935, 2829, 1730, 1283,
1101; 1H NMR (500 MHz, CDCl3) δ 7.40–7.26 (m, 5H, ArH), 6.14 (s, 1H,
H-6), 4.81–4.76 (m, 2H, H-1,4), 4.26 (d, J= 10.3 Hz, 1H, H-5), 4.09–4.06
(m, 1H, H-5’), 3.10–3.05 (m, 1H, H-3), 2.65–2.60 (m, 1H, H-2), 2.06 (s,
3H, –COCH3), 1.74–1.68 (m, 1H, H-2’); 13C NMR (125 MHz, CDCl3) δ
170.28, 140.15, 128.59, 128.58, 128.08, 126.16, 103.48, 83.06, 82.58,
74.22, 51.51, 39.84, 21.35; HRMS calcd for C14H16NaO4 [M + Na]+
271.0946, found 271.0941.
chromatography to afford compound 13 as a colorless liquid: Yield = 85
mg, 76%; Rf = 0.4 (9/1 hexane/EtOAc);
= +6.18° (c = 1.03, CH2Cl2);
IR (ṽmax/cm−1) 3416, 2958, 2930, 1452, 1109; 1H NMR (400 MHz, CDCl3)
δ 7.32–7.25 (m, 4H), 5.01 (t, J = 7.1 Hz, 1H), 3.81–3.78 (m, 1H), 3.69–
3.63 (m, 2H), 2.42 (br s, 1H), 2.23–1.95 (m, 3H), 1.09 (d, J = 6.7 Hz, 3H);
13C NMR (100 MHz, CDCl3) δ 143.13, 128.46, 127.46, 125.96, 87.25,
79.85, 64.08, 42.75, 34.37, 17.71; HRMS calcd for C13H15F3O2 [M + Na]+
260.1024, found 260.1021.
(2R,3S,E)-3-(Benzyloxy)-2-hydroxy-6-(trimethylsilyl)hex-4-en-1-yl
pivalate (15):
The alcohol 14 (300 mg, 1.02 mmol) was dissolved in dry
dichloromethane (5 mL), and Grubbs’ second generation catalyst (43 mg,
0.05 mmol) was added. The solution was refluxed for 5 h, and the solvent
removed under a vacuum. The crude residue was purified by column
chromatography gave 15 as a dark black thick liquid; Yield = 335 mg,
((2S,3R,5R)-3-(Hydroxymethyl)-5-(4-
(trifluoromethyl)phenyl)tetrahydrofuran-2-yl)methyl pivalate (11):
The aldehyde 8c (500 mg, 1.72 mmol) was dissolved in dry MeOH (5
mL) and cooled to 0 °C. Then, NaBH4 (137 mg, 3.44 mmol) was added to
the stirred reaction mixture in portions over 10 min, and stirring continued
for 1 h. Subsequently, aqueous NH4Cl (10 mL) was added dropwise to
the reaction mixture until the effervescence ceased. Extraction was done
using CH2Cl2 (3 × 10 mL), and the extracts were washed with brine (1 ×
15 mL) and dried over Na2SO4. Removal of solvent under vacuum
86%; Rf = 0.4 (9/1 hexane/EtOAc);
= +13.02° (c = 0.23, CH2Cl2); IR
(ṽmax/cm−1) 3477, 2957, 2904, 1731, 1093; 1H NMR (400 MHz, CDCl3) δ
7.35–7.25 (m, 5H), 5.79–5.71 (m, 1H), 5.34–5.28 (m, 1H), 4.62 (d, J =
11.8 Hz, 1H), 4.34 (d, J = 11.8 Hz, 1H), 4.20–4.11 (m, 2H), 3.91–3.86 (m,
1H), 3.76 (dd, J = 8.7, 5.1 Hz, 1H), 2.36 (d, J = 4.2 Hz, 1H), 1.63–1.54 (m,
2H), 1.18 (s, 9H), 0.05 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 178.66,
138.28, 135.04, 128.50, 127.91, 127.73, 124.08, 80.96, 72.09, 69.84,
65.27, 38.88, 27.27, 23.44, -1.76; HRMS calcd for C21H34NaO4Si [M +
Na]+ 401.2124, found 401.2122.
furnished
chromatography to give 11 as a colorless liquid; Yield = 307 mg, 61%; Rf
0.3 (8/2 hexane/EtOAc); –29.88° (c 0.20, CH2Cl2); IR
a
crude residue which was subjected to column
=
=
=
(ṽmax/cm−1) 3441, 2970, 2873, 1728, 1480; 1H NMR (400 MHz, CDCl3) δ
7.35–7.26 (m, 4H), 4.98 (dd, J = 7.9, 7.3 Hz, 1H), 4.37–4.27 (m, 2H),
4.11–4.07 (m, 1H), 3.80–3.70 (m, 2H), 2.43–2.34 (m, 1H), 2.22–2.16 (m,
1H), 2.04–1.96 (m, 1H), 1.87 (br s, 1H), 1.23 (s, 9H); 13C NMR (125 MHz,
CDCl3) δ 178.93, 142.58, 128.48, 127.55, 125.78, 80.65, 80.44, 66.26,
64.37, 43.60, 39.03, 37.93, 27.39; HRMS calcd for C18H23F3NaO4 [M +
Na]+ 383.1446, found 383.1443.
((2R,3S,5R)-3-(Benzyloxy)-5-(p-tolyl)-4-vinyltetrahydrofuran-2-
yl)methyl pivalate (16):
Pale yellow liquid; Yield = 182 mg, 84%; Rf = 0.4 (9/1 hexane/EtOAc); IR
(ṽmax/cm−1) 2925, 2855, 1730, 1284, 1160; 1H NMR (400 MHz, CDCl3,
mixture of diastereomers (/ = 0.8:1)
δ 7.37–7.09 (m, 18H, both
isomers), 6.09–6.00 (m, 1H, minor isomer), 5.46–5.37 (m, 1H, major
isomer), 5.24–5.23 (m, 1H, major isomer), 5.14–5.11 (m, 1H, minor
isomer), 5.05– 4.87 (m, 5H, both isomers), 4.67–4.52 (m, 4H, both
isomers), 4.38–4.35 (m, 1H, major isomer), 4.31–4.30 (m, 2H, both
isomers), 4.24–4.16 (m, 2H, both isomers), 4.02 (dd, J = 5.8, 2.1 Hz, 1H,
minor isomer), 3.91–3.89 (m, 1H, major isomer), 3.17–3.13 (m, 1H, major
isomer), 2.68 (td, J = 9.5, 5.8 Hz, 1H, major isomer), 2.32 (s, 3H, minor
isomer), 2.31 (s, 3H, major isomer), 1.22 (s, 18H, both isomers); 13C
NMR (100 MHz, CDCl3) δ 178.48, 178.37, 138.01, 137.82, 137.50,
136.95, 136.73, 136.21, 135.59, 132.64, 128.98, 128.79, 128.63, 128.57,
128.02, 127.89, 127.64, 126.43, 126.29, 119.26, 117.04, 85.80, 84.22,
83.66, 82.20, 81.85, 81.74, 72.07, 64.80, 64.12, 56.95, 55.03, 38.94,
27.38, 27.35, 21.28; HRMS calcd for C26H36NO4 [M + NH4]+ 426.2644,
found 426.2643.
((2S,3S,5R)-3-(Iodomethyl)-5-(4-
(trifluoromethyl)phenyl)tetrahydrofuran-2-yl)methyl pivalate (12):
To a solution of compound 11 (300 mg, 0.83 mmol) in toluene (10 mL)
were added PPh3 (656 mg, 2.5 mmol), imidazole (170 mg, 2.5 mmol) and
iodine (632 mg, 2.5 mmol). The reaction mixture was stirred at 90 °C for
2 h. After completion of the reaction (confirmed by TLC) toluene was
evaporated under reduced pressure, the residue was dissolved in CH2Cl2
(8 mL), washed with saturated Na2S2O3 (2 x 5 mL) (to quench the
unreacted iodine), brine (1 x 5 mL) and dried over Na2SO4. The solvent
was then removed in vacuo and the residue purified by flash column
chromatography to afford the compound 12 as a colorless liquid. Yield =
373 mg, 91%; Rf = 0.9 (9/1 hexane/EtOAc);
= –9.71° (c = 0.46,
CH2Cl2); IR (ṽmax/cm−1) 2970, 2871, 1729, 1282, 1157; 1H NMR (400
MHz, CDCl3) δ 7.33–7.26 (m, 4H), 5.03 (dd, J = 8.3, 6.9 Hz, 1H), 4.29–
4.28 (m, 2H), 4.02 (dt, J = 5.7, 4.4 Hz, 1H), 3.3–3.26 (m, 2H), 2.54–2.46
(m, 1H), 2.26–2.19 (m, 1H), 2.13–2.05 (m, 1H), 1.24 (s, 9H); 13C NMR
(125 MHz, CDCl3) δ 178.45, 142.07, 128.51, 127.67, 125.69, 82.59,
79.67, 65.25, 43.65, 42.48, 38.99, 27.40, 8.47; HRMS calcd for
((2R,3S,4R,5R)-3-(Benzyloxy)-5-(p-tolyl)-4-vinyltetrahydrofuran-2-
yl)methanol (17a):
Compound 17a was prepared from 16 (200 mg, 0.48 mmol) following the
same procedure as was used for the preparation of compound 9.
Colorless liquid; Yield = 68 mg, 43%; Rf = 0.5 (8/2 hexane/EtOAc);
+16.28° (c = 0.47, CH2Cl2); IR (ṽmax/cm−1) 3433, 2922, 2868, 1454, 1093;
1H NMR (400 MHz, CDCl3) δ 7.38–7.08 (m, 9H, ArH), 5.45–5.34 (m, 1H,
H-6), 5.24 (d, J = 6.4 Hz, 1H, H-1), 4.97–4.86 (m, 2H, H-7,7’), 4.66 (d, J =
11.7 Hz, 1H, –CH2Ph), 4.54 (d, J = 11.7 Hz, 1H, –CH2Ph), 4.08–4.03 (m,
1H, H-4), 3.94–3.88 (m, 2H, H-3&5), 3.75 (dd, J = 11.9, 5.2 Hz, 1H, H-5),
3.17–3.12 (m, 1H, H-2), 2.31 (s, 3H), 2.19 (br s, 1H); 13C NMR (100 MHz,
=
C
18H22F3INaO3 [M + Na]+ 493.0463, found 493.0463.
((2S,3S,5R)-3-Methyl-5-(4-(trifluoromethyl)phenyl)tetrahydrofuran-2-
yl)methanol (13):
To a stirred suspension of LiAlH4 (48 mg, 1.49 mmol) in THF (2 mL) was
added compound 12 (200 mg, 0.42 mmol) in THF (1 mL) at 0 oC. After
completion of addition, the reaction mixture was stirred at room
temperature for 2 h, cooled to 0 oC and quenched with ethyl acetate
followed by aqueous NH4Cl solution. After 15 min of stirring at room
temperature, the reaction mixture was filtered through a celite® pad,
washed with ethyl acetate (3 x 5 mL) and the filtrate evaporated under
vacuum. The residue was purified through silica gel column
CDCl3)
δ 137.99, 136.81, 136.08, 135.56, 128.82, 128.58, 127.95,
127.84, 126.39, 116.98, 85.51, 84.37, 82.44, 72.09, 63.08, 55.05, 21.25;
HRMS calcd for C21H24NaO3 [M + Na]+ 347.1623, found 347.1620.
((2R,3S,4S,5R)-3-(Benzyloxy)-5-(p-tolyl)-4-vinyltetrahydrofuran-2-
yl)methanol (17b):
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10.1002/ejoc.201801318
European Journal of Organic Chemistry
10
Colorless liquid; Yield = 55 mg, 35%; Rf = 0.5 (8/2 hexane/EtOAc);
=
Dostie, M. Prévost, P. Mochirian, K. Tanveer, N. Andrella, A. Rostami,
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X.-F. Ren, N. C. Chaudhuri, P. L. Paris, S. Rumney, E. T. Kool, J. Am.
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Eric T. Kool, Synlett 1997, 4, 341–347.
+52.17° (c = 1.51, CH2Cl2); IR (ṽmax/cm−1) 3534, 2976, 2863, 1470, 1010;
1H NMR (400 MHz, CDCl3) δ 7.38–7.12 (m, 9H, ArH), 6.08–5.98 (m, 1H,
H-6), 5.13–5.10 (m, 1H, H-7), 4.96–4.92 (m, 1H, H-7’), 4.86 (d, J = 9.9 Hz,
1H, H-1), 4.61–4.53 (m, 2H, –CH2Ph), 4.20– 4.17 (m, 1H, H-4), 4.04 (dd,
J = 6.3, 2.8 Hz, 1H, H-3), 3.78–3.75 (m, 1H, H-5), 3.68–3.64 (m, 1H, H-
5’), 2.70 (td, J = 9.4, 6.5 Hz, 1H, H-2), 2.32 (s, 3H, –CH3), 2.15 (br s, 1H);
13C NMR (100 MHz, CDCl3) δ 138.15, 137.75, 136.64, 132.85, 129.11,
128.54, 127.85, 127.74, 126.68, 119.08, 84.64, 84.39, 82.93, 72.08,
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C
21H24NaO3 [M + Na]+ 347.1623,
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Acknowledgements ((optional))
We thank the Department of Science and Technology, New
Delhi, India, for
a J. C. Bose National Fellowship (No.
SR/S2/JCB-26/2010) to Y. D. V., S. D., A. C. thanks the Council
of Scientific and Industrial Research, New Delhi.
Keywords: D-Mannitol • Prins reaction • C-furanosides •
Protecting groups • Glycosylation
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10.1002/ejoc.201801318
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European Journal of Organic Chemistry
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Entry for the Table of Contents (Please choose one layout)
Layout 2:
FULL PAPER
C-Furanosides*
Sateesh Dubbu, Anirban Bardhan, Ande
Chennaiah and Yashwant D. Vankar*
Page No. – Page No.
A Cascade of Prins Reaction and
Pinacol-Type Rearangement: Access
to 2,3-Dideoxy-3C-Formyl -C-
Aryl/Alkyl Furanosides and 2-Deoxy-
2C-Branched -C-Aryl Furanoside
Studies toward synthesis of the 2,3-dideoxy-3C-formyl -C-aryl/alkyl furanosides
and 2-deoxy-2C-branched -C-aryl furanoside were described using D-mannitol
derived homoallylic alcohols with carbonyl compounds in the presence of BF3•OEt2
as a catalyst.
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