Synthesis and electrophilic cyclization reactions of diphenyl 3-methylpenta-1,2,4-trienyl phosphine oxide

Article abstract of DOI:10.1080/00397911.2011.609957

Diphenyl 3-methyl-penta-1,2,4-trienyl phosphine oxide can be readily prepared via an atom-economical [2,3]-sigmatropic rearrangement of the mediated alkenynyl phosphinite formed in situ by reaction of 3-methylpent-1-en-4-yn-3-ol with diphenylchlorophosphi

Full text of DOI:10.1080/00397911.2011.609957

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Synthesis and Electrophilic
Cyclization Reactions of Diphenyl 3-
Methylpenta-1,2,4-trienyl Phosphine
Oxide
Ivaylo K. Ivanov a & Valerij C. Christov a
a Department of Organic Chemistry and Technology, Faculty of
Natural Sciences, Konstantin Preslavsky University of Shumen,
Shumen, Bulgaria
Accepted author version posted online: 09 May 2012.Version of
record first published: 21 Dec 2012.
To cite this article: Ivaylo K. Ivanov & Valerij C. Christov (2013): Synthesis and Electrophilic
Cyclization Reactions of Diphenyl 3-Methylpenta-1,2,4-trienyl Phosphine Oxide, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry,
43:6, 800-809
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Synthetic Communications1, 43: 800–809, 2013
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397911.2011.609957
SYNTHESIS AND ELECTROPHILIC CYCLIZATION
REACTIONS OF DIPHENYL 3-METHYLPENTA-
1,2,4-TRIENYL PHOSPHINE OXIDE
Ivaylo K. Ivanov and Valerij C. Christov
Department of Organic Chemistry and Technology, Faculty of Natural
Sciences, Konstantin Preslavsky University of Shumen, Shumen, Bulgaria
GRAPHICAL ABSTRACT
Abstract Diphenyl 3-methyl-penta-1,2,4-trienyl phosphine oxide can be readily prepared via
an atom-economical [2,3]-sigmatropic rearrangement of the mediated alkenynyl phosphi-
nite formed in situ by reaction of 3-methylpent-1-en-4-yn-3-ol with diphenylchloropho-
sphine. Electrophilic cyclization reactions of the vinylallenyl phosphine oxide prepared
were investigated as it was established that the reactions proceeded with formation of vari-
ous heterocyclic or highly unsaturated compounds with participation of the allenic and/or
1,3-dienic part of the vinylallenic system with neighboring group participation of phosphoryl
and/or vinylic group.
Supplemental materials are available for this article. Go to the publisher’s online edition
of Synthetic Communications1 to view the free supplemental file.
Keywords 2,5-Dihydro-1,2-oxaphosphole; electrophilic cyclization; neighboring group
participation; selenophene; thiophene; 3-vinylallenyl phosphine oxide
INTRODUCTION
In the past three decades, synthesis and use of allene derivatives have been
expanded in preparative organic chemistry. The presence of two p electron clouds
separated by a single sp hybridized carbon atom is the identifying structural
Received July 20, 2011.
Dedicated to Professor Dr. Toru Minami from Kyushu Institute of Technology, Kitakyushu,
Japan, on the occasion of his 70th birthday.
Address correspondence to Valerij C. Christov, Department of Organic Chemistry and
Technology, Faculty of Natural Sciences, Konstantin Preslavsky University of Shumen, 115
Universitetska str., BG-9700, Shumen, Bulgaria. E-mail: vchristo@shu-bg.net
800

CYCLIZATIONS OF 3-VINYLALLENYL PHOSPHINE OXIDE
801
characteristic of allenes, and it is this unique structural and electronic arrangement
that is responsible for the extraordinary reactivity profile displayed by allenic com-
pounds.[1] The synthetic potential of functionalized allenes has been explored exten-
sively in recent years, and this has led to the development of novel methods for the
construction of a variety of functionalized heterocyclic and carbocyclic systems.[2]
An impressive number of heterocyclic systems have been prepared from allenic start-
ing materials.
One of the characteristic reactions of the allenes is the electrophilic addition
reactions in which the addition products of the reagent to the one and=or other dou-
ble bond of the allenic system are usually obtained.[3] Functionalized allenes are very
interesting substrates as a material of choice to study the electrophilic addition reac-
tions on the carbon–carbon double bonds.[4–6] Unlike the allenic hydrocarbons, the
presence of a functional group linked to the allenic system considerably changes the
course of the reactions with electrophilic reagents. It has been shown[4–6] that the
reactions proceeded with cyclization of the allenic system bearing a functional group
to give heterocyclic compounds in most cases. It makes the investigations on the
functionalized allenes, more specifically in studying their reactions with electrophilic
reagents, quite an interesting and topical task.
Recently, we developed the electrophilic cyclization reactions of 1- and 3-viny-
lallenyl sulfoxides[7] and sulfones.[8] In all the cases, the electrophilic atom has been
introduced to the central carbon atom of the allene moiety and the reactions
proceeded with participation of the allenic and=or 1,3-dienic part of the vinylallenic
system with neighboring group participation of sulfinyl (sulfonyl) and=or vinylic
group.[7,8]
Literature data on the electrophilic addition reactions to phosphorylated
allenes (phosphonates, phosphinates, and phosphine oxides) show that various
five-membered heterocyclizations proceed in most cases.[4,6,9–12] On the other hand,
the reactions of the 1,2,4- and 1,3,4-alkatrienephosphonates with electrophiles lead
to the synthesis of various heterocyclic compounds. For example, the halogenation
reactions afford the 3- or 5-vinyl-substituted 2,5-dihydro-1,2-oxaphospholes,[13,16]
while the interaction with sulfenyl[14,16] and selenenyl[15,16] chlorides gives the
thiophene- or selenophene-2- or 3-phosphonates.
There are methods[17] for the synthesis of phosphorus-containing allenes
(phosphonates,[18] phosphinates,[19] and phosphine oxides[20]) including reactions
of a-alkynols with chloride-containing derivatives of phosphorus acids followed by
[2,3]-sigmatropic rearrangement.
As a part of our long-standing program on the synthesis and cyclization reac-
tions of sulfur- and phosphorus-functionalized vinylallenes, we now report the
results on the synthesis of diphenyl 3-methyl-penta-1,2,4-trienyl phosphine oxide
and the reactions with some electrophilic reagents for study of the electrophilic
cyclization reactions.
DISCUSSION
Since its discovery five decades ago,[18a,19a,19b] the reversible interconversion of
propargylic phosphites, phosphonites, and phosphinites to allenyl phosphonates,
phosphinates, and phosphine oxides has become one of the most studied and

802
I. K. IVANOV AND V. C. CHRISTOV
synthetically useful [2,3]-sigmatropic rearrangements. Numerous synthetic applica-
tions of the rearrangement have been reported, including its use in the synthesis of
allenic steroids as substrate-induced inactivation of aromatase,[21a] in the efficient
synthesis of (2R)-2-amino-5-phosphonopentanoic acid (AP5) as a powerful and
selective N-methyl-D-aspartate (NMDA) antagonist,[21b] in the preparation of the
phosphonate analogs of phosphatidyl derivatives,[21c,21d] and in the synthesis of
new acyclic analogs of nucleotides containing a purine or pyrimidine moiety and
an allenic skeleton.[21e,21f]
Our strategy for the synthesis of diphenyl 3-methyl-penta-1,2,4-trienyl
phosphine oxide 2, using our experience on the preparation of the vinylallenyl
sulfoxides[7] and sulfones,[8] relies on the well-precedented [2,3]-sigmatropic shift of
propargylic phosphinites to allenyl phosphine oxides.[20]
Diphenyl 3-methyl-penta-1,2,4-trienyl phosphine oxide 2 can be readily
prepared via an atom-economical [2,3]-sigmatropic rearrangement of the mediated
alkenynyl phosphinite A formed in situ by reaction of the 3-methylpent-1-en-4-
yn-3-ol 1 with diphenylchlorophosphine in the presence of triethylamine according
to Scheme 1.
After a conventional workup, the resulting compound 2 was isolated by col-
1
umn chromatography as a pale yellow oil and identified by H and 13C NMR and
infrared (IR) spectra as well as by elemental analysis.
The vinylallenyl phosphine oxide 2 isolated in preparative amounts allowed us
to study its chemical behavior in the reactions with electrophilic reagents. From gen-
eral considerations as well as from the literature data on the electrophilic addition
reactions[22] to phosphorylated allenes,[4] 1,2,4- and 1,3,4-alkatrienephospho-
nates,[13–16] and vinylallenyl sulfoxides[7] and sulfones,[8] the following pathways of
the reactions could be assumed:
i. Attack of the reagent on the C2-C3 double bond with formation of 2,3-adduct;
ii. Attack of the reagent on the C2-C3 double bond with formation of 1,3-alkadienic
system and preparation of 2,5-adduct;
iii. Attack of the reagent on the C2-C3 double bond of the trienic system and follow-
ing neighboring group participation of the internal nucleophile (phosphoryl
group) and ring closure to five-membered cyclic compound;
iv. Attack of the reagent on the C2-C3 double bond of the trienic system and follow-
ing neighboring group participation of the vinylic double bond and ring closure
to cyclic compound;
v. Attack of the reagent on the C1-C2 double bond with formation of 1,2-adduct;
and
vi. Elimination reactions after realization of some of the above mentioned pathways
(i–v).
Scheme 1. Synthesis of diphenyl 3-methyl-penta-1,2,4-trienyl phosphine oxide 2.

CYCLIZATIONS OF 3-VINYLALLENYL PHOSPHINE OXIDE
803
We initially examined the halogenation reaction of the diphenyl 3-methyl-
penta-1,2,4-trienyl phosphine oxide 2 with sulfuryl chloride. According to our pre-
vious experimental results on the electrophilic cyclization reactions of functionalized
vinylallenes,[7,8] dichloromethane was a good solvent for electrophilic addition reac-
tions of allenes. When CH2Cl2 was used as the solvent, the diphenyl 3-methyl-penta-
o
1,2,4-trienyl phosphine oxide 2 reacted with SO2Cl2 at ꢀ20 C to give a mixture of
(1E)-2-chloro-3-methylene-penta-1,4-dienyl diphenyl phosphine oxide 3a and (1E)-2-
chloro-1-(diphenylphosphoryl)-3-methyl-penta-1,4-dien-3-ol 4a in the ratio of 3a=4a
being 1.5=1 in 66% yield, according to the reaction sequence outlined in Scheme 2.
The resulting compounds E-3a and E-4a were isolated by column chromato-
1
graphy as oils and identified by H and 13C NMR and IR spectra as well as by
elemental analysis.
Obviously, the hydroxyl group in E-4a was formed from the water in the reac-
tion media, as it was shown by Ma and coworkers in the iodohydroxylation,[9] fluor-
ohydroxylation,[10] and selenohydroxylation[11] reactions of allenyl phophine oxides
with iodine, selectfluor, and benzeneselanyl chloride. A mechanistic rationale for the
formation of the trienyl phosphine oxide E-3a in the elimination reaction of hydro-
gen chloride and the 3-hydroxy-1,4-dienyl phosphine oxide E-4a in hydrolysis reac-
tion would appear not to be straightforward. The result reported previously can be
considered in terms of the following two assumptions:
i. Intermediate formation of the C3-carbenium ion and following elimination of
hydrogen chloride after an attack of chloride anion on the methyl group to give
E-3a as has been shown by Horner and Binder[23] and Braverman and Reis-
man[24] in the case of halogenation of allenyl sulfoxides and sulfones or following
water addition to C3 atom of the carbenium ion to afford E-4a; and
ii. Deprotonation to give E-3a after an attack of chloride anion on the methyl group
and the C5-O bond cleavage or water molecule attacks the positively charged
phosphorus atom to cleave the P-O bond, forming E-4a, both in the stage of
the in situ–generated cyclic 2,5-dihydro-1,2-oxaphosphol-2-ium chloride as Ma
and coworkers[9–11] and Saalfrank and coworkers[25] supposed in the reactions
of the allenyl phosphine oxides with electrophilic reagents.
The results reported confirm our second assumption that the reaction of viny-
lallenyl phosphine oxide 2 with sulfuryl chloride leading to the formation of a mix-
ture of E-3a and E-4a probably proceeds through the cyclic phosphonium chloride,
which corroborates our results on the reactions of the vinylallenyl phosphine oxide 2
with bromine and iodine (Scheme 3), sulfanyl (Scheme 4), and selanyl (Scheme 5)
chlorides.
Scheme 2. Chlorination reaction of diphenyl 3-methyl-penta-1,2,4-trienyl phosphine oxide 2 with sulfuryl
chloride.

804
I. K. IVANOV AND V. C. CHRISTOV
Scheme 3. Bromination and iodination reactions of diphenyl 3-methyl-penta-1,2,4-trienyl phosphine
oxide 2.
Moreover, the E-configuration of the triene E-3a and the diene E-4a was
assigned on the base of the chemical shift values[26] of the olefinic proton at C1 atom
1
and of the C1 atom in the H and 13C NMR spectra. In addition, the intermediate
formation of the cyclic 2,5-dihydro-1,2-oxaphosphol-2-ium chloride predetermines
the configuration of the products E-3a and E-4a.
In contrast to the chlorination, the bromination and iodination reactions of the
alkatrienyl phosphine oxide 2 were carried out with five-membered heterocyclization
=
=
of the allenic system of double bonds bearing a phosphoryl group (C C ¼ C-P O)
to give 2,5-dihydro-1,2-oxaphosphol-2-ium bromide 5b and iodide 5c in 75% and
68% yields as shown in Scheme 3.
The results reported in Scheme 3 confirm our second assumption that the reac-
tion of the vinylallene 3 with sulfuryl chloride probably proceeds through the
1,2-oxaphosphol-2-ium chloride. Another confirmation for that is the next results
on the electrophilic reactions of 2 with sulfanyl and selanyl chlorides.
Surprisingly, reaction of the 1,2,4-trienyl phosphine oxide 2 with methane- and
benzenesulfanyl chlorides proceeds with two types of electrophilic cyclization by
neighboring group participation of both the vinylic double bond and the phosphine
oxide group to give mixtures of the 2-(diphenylphosphorylmethyl)-thiophene 6, the
4-methyl(phenyl)sulfanyl-2,5-dihydro-1,2-oxaphosphol-2-ium chlorides 5d, and e,
and their dehydrochlorination products—the (1E)-3-methylene-2-methyl(phenyl)-
sulfanyl-penta-1,4-dienyl diphenyl phosphine oxides 3d, and e in 75–78% overall
yields according to the sequence outlined in Scheme 4.
The products 6, 5d, and 5e and E-3d, and e were isolated by column chroma-
1
tography as oils and identified by H and 13C NMR and IR spectra as well as by
elemental analysis.
In a similar way, a ca. 4.4:1 mixture of the 2-(diphenylphosphorylmethyl)-
selenophene 7 and the 4-phenylselanyl-2,5-dihydro-1,2-oxaphosphol-2-ium chloride
5f was obtained with 76% overall yield from the reaction of the vinylallenyl
o
phosphine oxide 2 with benzeneselanyl chloride in dry dichloromethane at ꢀ10 C
as outlined in Scheme 5.
Scheme 4. Sulfanylation reaction of diphenyl 3-methyl-penta-1,2,4-trienyl phosphine oxide 2.

CYCLIZATIONS OF 3-VINYLALLENYL PHOSPHINE OXIDE
805
Scheme 5. Selanylation reaction of diphenyl 3-methyl-penta-1,2,4-trienyl phosphine oxide 2.
Resulting selenophene 7 and oxaphosphole 5f were isolated by column chro-
matography and identified by 1H and 13C NMR and IR spectra as well as by elemen-
tal analysis. The obtained compounds 7 and 5f contain the isotope 77Se, which is
magnetically active and interacts with other nuclei. This interaction becomes evident
with the protons and carbons of the neighboring groups, which exhibit symmetric
1
satelite signals of the main signal in the H and 13C NMR spectra.[27]
On the basis of previous results,[7,8] a plausible is proposed (Scheme 6). The
initial act is the attack of electrophilic sulfur or selenium on the most nucleophilic
atom of the trienic system of p bonds (C2) with the formation of the cyclic onium
(thiiranium or seleniranium) ions B after an attack on the relatively electron-rich
C2-C3 double bond. The ions B are in the plane of the p bond of the vinyl group
(s-cis conformation), and for this reason, B are easily transformed into the more
stable five-membered cyclic ions C. Further, the ions C undergo elimination of
methyl or phenyl chloride, [1,5]-prototropic shift, and aromatization to give the thio-
phene 6 or selenophene 7. The five-membered cyclic phosphonium chlorides 5d–f is
formed via neighboring group participation of the oxygen atom of the diphenyl
phosphine oxide functionality in the stage of ions B formation.
The simultaneous realization of the both heterocyclization processes is connec-
ted with introduction of the allenic and 1,3-dienic parts of the trienic system into the
reaction course. This fact is obviously a result the ability of the sulfur and selenium
to form cyclic ions,[28] which are further transformed into five-membered hetero-
cyclic compounds.
In terms of reaction mechanism of the trienyl phosphine oxides E-3a, d, and e
and the 3-hydroxy-1,4-dienyl phosphine oxide E-4a formation, we carried out the
elimination and hydrolysis reactions of the cyclic 2,5-dihydro-1,2-oxaphosphol-2-
ium halides 5b–f. Heating at reflux of the cyclic phosphonium salts 5 in 1,2-dichlor-
oethane for 3 h provoked elimination of hydrogen halide and C5-O bond cleavage in
Scheme 6. Proposed mechanism of sulfanylation and selanylation reactions. (Figure is provided in color
online.)

806
I. K. IVANOV AND V. C. CHRISTOV
the ring with generation of the 3-methylene-penta-1,4-dienyl phosphine oxides E-3b–
e in good yield (64–68%) as shown in Scheme 7.
The attempts at an elimination reaction of hydrogen chloride of the
4-phenylselanyl-2,5-dihydro-1,2-oxaphosphol-2-ium chloride 5f were not successful.
In all cases, no traces of the expected 1,4-dienyl phosphine oxide 3f were detected.
Instead complex mixtures of decomposed products were obtained.
The hydrolysis reaction of the 2,5-dihydro-1,2-oxaphosphol-2-ium halides 5b–f
occurs with the water molecule attack at the positively charged phosphorus atom to
cleave the P-O bond,[9–11] which results in the formation of final (1E)-1-
(diphenylphosphoryl)-3-methyl-penta-1,4-dien-3-ols 4b–f in 63–70% yields, accord-
ing to the sequence outlined in Scheme 7.
In conclusion, we note the following points from this investigation:
i. Diphenyl 3-methyl-penta-1,2,4-trienyl phosphine oxide 2 can be readily prepared
via an atom economical [2,3]-sigmatropic rearrangement of the mediated alkeny-
nyl phosphinite formed in situ by reaction of 3-methylpent-1-en-4-yn-3-ol with
diphenylchlorophosphine.
ii. Electrophilic cyclization reactions of the vinylallenyl phosphine oxide 2 were
investigated as it was established that the reactions proceeded with formation
of various heterocyclic and=or highly unsaturated compounds with participation
of the allenic and=or 1,3-dienic part of the vinylallenic system with neighboring
participation of phosphoryl and=or vinylic group.
iii. Elimination and hydrolysis reactions of the cyclic 2,5-dihydro-1,2-oxaphosphol-
2-ium salts 5b–f formed proceed with the C5-O or P-O bond cleavage in the ring
with generation of the highly unsaturated phosphine oxides E-3b–e or E-4b–f.
iv. The diphenyl 3-methyl-penta-1,2,4-trienyl phosphine oxide 2 is a versatile
synthone for heterocyclic and unsaturated compounds in organic synthesis.
Results of an initial investigation of the physiological activity of the com-
pounds prepared were encouraging and the activity of selected compounds is now
under investigation. A continuation of these studies toward the synthesis and
Scheme 7. Opening ring reactions of 2,5-dihydro-1,2-oxaphosphol-2-ium salts 5b-f. (Figure is provided in
color online.)

CYCLIZATIONS OF 3-VINYLALLENYL PHOSPHINE OXIDE
807
electrophilic cyclization reactions of other functionalized vinylallenes is currently in
progress in our laboratory.
EXPERIMENTAL
Synthesis of 3-Methylpenta-1,2,4-trienyl Diphenyl Phosphine Oxide 2
A solution of freshly diphenylchlorophosphine (6.62 g, 30 mmol) in dry
dichloromethane (20 mL) was added dropwise with stirring to a solution of
3-methylpent-1-en-4-yn-3-ol 1 (3.36 g, 30 mmol) and triethylamine (3.34 g, 33 mmol)
o
in dry dichloromethane (50 mL) at ꢀ70 C. The reaction mixture was stirred for 1 h
at the same temperature and for 3 h at rt, washed with water (50 ml) and 2 N HCl,
and extracted with ether, and the extract was washed with saturated NaCl and dried
over anhydrous sodium sulfate. Evaporation yielded the crude product 2, which was
purified by column chromatography on silica gel. Pale yellow oil, yield: 59%.
Electrophilic Cyclization Reactions of the
3-Methylpenta-1,2,4-trienyl Diphenyl Phosphine Oxide 2
A solution of electrophilic reagent (sulfuryl chloride, bromine, iodine, methane-
sufanyl chloride, benzenesulfanyl chloride, and benzeneselanyl chloride) (10 mmol) in
dry dichloromethane (10 mL) was added dropwise with stirring to a solution of triene
2 (2.80 g, 10 mmol) in dry dichloromethane (20 mL) at ꢀ20 oC. The reaction mixture
was stirred for 1 h at the same temperature and for 3 h at rt. The solvent was removed
using a rotatory evaporator, and the residue was purified by column chromatography
on silica gel (Kieselgel Merck 60 F254) with ethyl acetate = heptane.
Elimination Reaction of the 2,2-Diphenyl-5-vinyl-
5-methyl-2,5-dihydro-1,2-oxaphosphol-2-ium Salts 5b–f
A solution of the cyclic phosphonium salts 5b–f (5 mmol) in dry 1,2-dichloro-
methane (10 mL) was refluxed with stirring for 3 h. The reaction mixture was stirred
for 1 h at rt and then extracted with ether, and the extract was washed with saturated
NaCl and dried over anhydrous sodium sulfate. Evaporation yielded the crude pro-
duct, which was purified by column chromatography on silica gel with ethyl acetate=
heptane as eluents.
Elimination Reaction of the 2,2-Diphenyl-5-vinyl-
5-methyl-2,5-dihydro-1,2-oxaphosphol-2-ium Salts 5b–f
A solution of the cyclic phosphonium salts 5b–f (5 mmol) in dry 1,2-dichloro-
methane (10 mL) was refluxed with stirring for 3 h. The reaction mixture was stirred
for 1 h at rt and then extracted with ether, and the extract was washed with saturated
NaCl and dried over anhydrous sodium sulfate. Evaporation yielded the crude pro-
duct, which was purified by column chromatography on silica gel with ethyl acetate=
heptane as eluents.

808
I. K. IVANOV AND V. C. CHRISTOV
Supplementary Material Available Online
Method of analysis, starting materials, and full spectroscopic and characteriza-
tion data including 1H and 13C NMR and IR spectral data and elemental analysis for
all new compounds and literature references to these data for known compounds are
listed.
ACKNOWLEDGMENTS
Support from the Research Fund of the Konstantin Preslavsky University of
Shumen (Projects No. RD-05-367 = 2010 and No. RD-05-137 = 2011) is acknowl-
edged. Special thanks to Hasan Hasanov for the technical help in the chromatogra-
phical separations.
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