Electrochemical selenium- and iodonium-initiated cyclisation of hydroxy-functionalised 1,4-dienes

Article abstract of DOI:10.3762/bjoc.11.18

The cobalt(I)-catalysed 1,4-hydrovinylation reaction of allyloxytrimethylsilane and allyl alcohol with substituted 1,3-dienes leads to hydroxy-functionalised 1,4-dienes in excellent regio- and diastereoselective fashion. Those 1,4-dienols can be converted

Full text of DOI:10.3762/bjoc.11.18

Electrochemical selenium- and iodonium-initiated cyclisation
of hydroxy-functionalised 1,4-dienes
Philipp Röse1, Steffen Emge1, Jun-ichi Yoshida2 and Gerhard Hilt*1
Full Research Paper
Open Access
Address:
Beilstein J. Org. Chem. 2015, 11, 174–183.
1Fachbereich Chemie, Philipps-Universität Marburg,
Hans-Meerwein-Str. 4, 35043 Marburg, Germany and 2Department of
Synthetic Chemistry and Biological Chemistry, Graduate School of
Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan
doi:10.3762/bjoc.11.18
Received: 27 November 2014
Accepted: 16 January 2015
Published: 28 January 2015
Email:
Gerhard Hilt* - hilt@chemie.uni-marburg.de
This article is part of the Thematic Series "Electrosynthesis".
Guest Editor: S. R. Waldvogel
* Corresponding author
Keywords:
© 2015 Röse et al; licensee Beilstein-Institut.
License and terms: see end of document.
cyclic ethers; cyclisation; 1,4-dienes; electrochemistry; iodonium;
selenium
Abstract
The cobalt(I)-catalysed 1,4-hydrovinylation reaction of allyloxytrimethylsilane and allyl alcohol with substituted 1,3-dienes leads to
hydroxy-functionalised 1,4-dienes in excellent regio- and diastereoselective fashion. Those 1,4-dienols can be converted into
tetrahydrofuran and pyran derivatives under indirect electrochemical conditions generating selenium or iodonium cations. The reac-
tions proceed in good yields and regioselectivities for the formation of single diastereomers.
Introduction
The reaction of terminal alkenes with 1,3-dienes under cobalt substructures in many natural compounds, pesticides and drugs
catalysis results in 1,4-dienes in a 1,4-hydrovinylation reaction. with antifungal and antibacterial properties [10-13]. For this
Besides cobalt, also other transition metals were described to purpose, we investigated a protocol for the straight forward syn-
undergo such transformations [1-4]. However, only for the thesis of 1,4-dienols which should be cyclised into the corre-
cobalt-catalysed reactions a regiodiverse reaction has been sponding tetrahydrofuran or pyran derivatives. With our sight
described where the carbon–carbon bond formation, either at set on efficient and atom economic organic reactions electro-
the terminal carbon of the double bond (C1) or on C2 was chemistry seems to be a powerful tool for the transformation of
formed, depending on the ligand system applied [5,6]. Besides those 1,4-dienols. Although it seems that all possible functional
the ozonolysis of the 1,4-dienes for the generation of 1,3-dicar- groups have been investigated in organic electrochemistry,
bonyl derivatives [7-9], these 1,4-dienes are in turn potential reports on electrochemical transformations of 1,4-dienes are
substrates for the synthesis of functionalised heterocycles. rare [14-17]. First attempts of a direct electrochemical conver-
Particularly, we were interested in the synthesis of tetrahydro- sion were not very successful, so that we turned our attention
furan and pyran derivatives. Those heterocycles are prevalent towards indirect electrochemical methods [18,19]. Among these
174

Beilstein J. Org. Chem. 2015, 11, 174–183.
we became interested in the electrochemical generation of could be generated from simple 1,3-dienes, such as 1,3-
reactive cations inducing a transformation of the 1,4-diene butadiene or 1-aryl-substituted 1,3-dienes 1, and TMS-protected
moiety. As a starting point we put our interest in electrochem- allylic alcohol (Scheme 1) for the synthesis of 1,4-dienols of
ical reactions using selenium cations. Several methods applying type 2.
electrochemically generated selenium cations with alkenes or
alkynes including seleno-etherification and lactonisation, epox- The cobalt-catalysed hydrovinylation reaction is highly regio-
idation and oxoselenylation sequences have been reported in the specific for the carbon–carbon bond formation which takes
last decades [20-27]. The reactions often proceed in a regio- and place exclusively at the internal carbon of the double bond of
stereoselective fashion and tolerate a wide range of functional- the terminal alkene (C2) and C4 of the 1-aryl-substituted 1,3-
ities.
diene. The key intermediate A in the reaction mechanism is
proposed to be a cobaltacycle which only allows the double
Next to selenium cation induced reactions we put our focus on bond generated from the 1,3-diene component to adopt a Z-con-
using halonium cations. The advantage of this type of reaction figuration. Accordingly, the products of type 2 are formed in
is its lower toxicity and the easy access towards the halonium high selectivity in terms of regio- and diastereomeric control.
source. Several reactions using bromonium- and iodonium
cations such as iodo-etherification, lactonisation or Friedel– The starting materials of type 1 were generated from the
Crafts alkylation reactions can be found in literature. However, aromatic aldehydes and allyltriphenylphosphonium bromide in
these procedures often use expensive or toxic halonium sources a Wittig reaction following a known protocol [53]. The syn-
like molecular bromine [10,28,29] or organic trihalide salts thesis of the 1,4-dienes was then accomplished utilising the
[30], N-bromosuccinimide or N-iodosuccinimide and its cobalt-catalyst precursor and reducing conditions in the pres-
derivatives [31-36], or more specialised reagents such as ence of zinc iodide for abstracting the bromide anions at room
bis(pyridinium)iodonium(I) tetrafluoroborate [37-39]. Next to temperature. The TMS-protected allylic alcohol was applied in
those, the in situ oxidation of halogenide ions with strong oxi- the cobalt-catalysed 1,4-hydrovinylation process with aryl-
dants such as oxone, Pb(IV), mCPBA, FeCl3 or H2O2 have substituted 1,3-dienes 1a–k because the use of allylic alcohol
been reported [40-45]. A more efficient and versatile method is itself led to significant lower yields (up to 30%). Only in case of
the electrochemical generation of halonium ions. Thereby, it is buta-1,3-diene, 2,3-dimethyl-1,3-butadiene and isoprene allyl
possible to accumulate the halonium ions in solution and to add alcohol could be used directly without decreasing the yield
those to a substrate in a separated process (“pool” method) [46- (Table 1, entries 12–14). The results of the 1,4-dienol syntheses
51] or to consume the halonium ions in situ in follow-up reac- are summarised in Table 1.
tions inside the cell [52].
The cobalt-catalysed hydrovinylation tolerates halide, ether,
Accordingly, we envisaged the generation of suitable starting ester, trifluoromethyl and heterocyclic substituents and gave the
materials via a cobalt-catalysed hydrovinylation reaction and desired products in acceptable to good yields over a two-step
investigated their in situ conversion via electrochemically reaction sequence of hydrovinylation and deprotection. Elec-
generated selenium- or iodonium cations.
tron-withdrawing and electron-donating groups as well as ster-
ically hindered aryl substituents are also accepted (see Table 1,
entries 7 and 9). The use of buta-1,3-diene and 2,3-dimethyl-
1,3-butadiene gave the 1,4-dienols in excellent yields (Table 1,
entries 12 and 13). When isoprene was used, the regioisomeric
products 2n and 2o were formed in good yields and acceptable
regioselectivity, with the carbon–carbon bond formation taking
place predominantly at the lower substituted end of the 1,3-
Results and Discussion
Cobalt-catalysed 1,4-hydrovinylation of allylic
alcohols
For the successful application of 1,4-dienes in the electrochem-
ical reactions, 1,4-dienes with additional internal nucleophiles,
such as an alcohol group, were envisaged and those 1,4-dienols
Scheme 1: Cobalt-catalysed 1,4-hydrovinylation.
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Beilstein J. Org. Chem. 2015, 11, 174–183.
Transformation of 1,4-dienols via electro-
diene moiety. These results demonstrate that the cobalt-cata-
lysed hydrovinylation reaction is a powerful tool for the generated selenium cations
straightforward synthesis of various 1,4-dienols of type 2 and The 1,4-dienols were transformed into cyclic phenylseleno-
the mild reaction conditions made it possible to generate and ethers by intramolecular cyclisation using selenium cations
isolate the products without isomerisation of the double bonds generated by indirect electrolysis. The reaction was carried out
towards undesired side-products.
by electrolysing a mixture of the 1,4-dienol, diphenyl disel-
Table 1: Results of the cobalt-catalysed 1,4-hydrovinylation reaction of TMS-protected allylic alcohol with 1,3-dienes of type 1.
Entry
1,3-Diene (1)
1,4-Dienol (2)
Yielda
60%
1
2
71%
3
4
81%
51%
5
6
7
8
69%
87%
64%
67%
176

Beilstein J. Org. Chem. 2015, 11, 174–183.
Table 1: Results of the cobalt-catalysed 1,4-hydrovinylation reaction of TMS-protected allylic alcohol with 1,3-dienes of type 1. (continued)
9
60%
10
11
59%
87%
12
13
92%b
90%b
89%
(2n:2o = 79:21)
14
aReaction conditions: (i) 1,3-diene (1.0 equiv), allyloxytrimethylsilane (1.2 equiv), CoBr2(dppe) (5–10 mol %), Zn powder (10–20 mol %), ZnI2
(10–20 mol %), CH2Cl2 (1 mL/mmol), rt, 12–16 h (ii) TBAF (1.1 equiv), THF, 0 °C, 3 h. bReaction conditions: 1,3-diene (1.0 equiv), allyl alcohol
(1.2–2.0 equiv), CoBr2(dppe) (5–10 mol %), Zn powder (10–20 mol %), ZnI2 (10–20 mol %), CH2Cl2 (1 mL/mmol), rt, 12–16 h.
enide and tetraethylammonium bromide in CH3CN at room ion with the 1,2-disubstituted double bond would lead to the
temperature in an undivided cell, using platinum foil electrodes furan-type products 3 or alternatively to pyran-type product 4.
(constant current 10 mA). In this investigation only diphenyl The results of the electrochemical selenoalkoxylation of the 1,4-
diselenide was used as selenium source. These reaction condi- dienols are summarised in Table 2.
tions led to the formation of products of type 3 as exclusive
diastereomers (Scheme 2).
The electrochemical selenoalkoxylation of the aryl-substituted
derivatives of type 2 (Table 2, entries 1–7) led exclusively to
The cyclisation of 2 could lead to a number of products. The the tetrahydrofuran derivatives 3 via a 5-exo-tet-type cyclisa-
PhSe+ cation could interact with the 1,1-disubstituted double tion in moderate to good yields. The products were generated in
bond and nucleophilic attack could lead to oxiran- or oxetan- diastereoselective fashion and the configuration of the formed
type products. On the other hand, the interaction of the PhSe+ diastereomer could be identified by 1H NMR experiments
Scheme 2: Electrochemical selenoalkoxylation of 2.
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Beilstein J. Org. Chem. 2015, 11, 174–183.
Table 2: Electrochemical selenoalkoxylation of 1,4-dienols 2a.
Entry
1
1,4-Dienol (2)
Furan (3) or pyran (4)
Yieldb
50%
2
3
4
82%
58%
68%
5
42%
90%
6
7
62%
86%
8
9
46% (3m)
47% (4m)
10% (3o+3o’)
58% (4n)
10
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Beilstein J. Org. Chem. 2015, 11, 174–183.
Table 2: Electrochemical selenoalkoxylation of 1,4-dienols 2a. (continued)
75%
(3p:4p =
1:2.5)
11
53%
(3q:4q =
1:1.4)
12
aReaction conditions: 1,4-dienol (0.5 mmol, 1.0 equiv), Ph2Se2 (0.5 equiv), Et4NBr (0.1 equiv), CH3CN (10 mL), rt, undivided cell, Pt/Pt, 10 mA,
6.67 mA/cm2. bOxidation of the alcohol could be observed in all reactions (less than 10%).
comparing a mixture of both diastereomers, synthesised by 1,4-dienols (2p and 2q) a preferred formation of the pyran
conventional selenoalkoxylation, with the electrochemically products was observed (Table 2, entries 11 and 12). However,
generated selenoether (see Supporting Information File 1). As a under no circumstances the previously discussed strained
side reaction the oxidation of the alcohol could be observed in epoxy-derivatives could be detected.
all reactions (less than 10%). Moreover, under electrochemical
Transformation of 1,4-dienols via electro-
conditions the simple methyl-substituted derivative 2l led to the
tetrahydrofuran-type product 3l in 86% yield (Table 2, entry 8) generated iodonium cations
while the reaction using PhSeBr under conventional methods In a similar approach we investigated the cyclisation of the 1,4-
gave the product in 76% yield and a diastereoselectivity of dienols 2 with in situ electrochemically generated iodonium
73:27 (threo:erythro). When alkyl-substituted 1,4-dienols are ions for the desired synthesis of iodoalkoxylated products of
used, the formation of tetrahydrofuran or pyran derivatives can type 5 (Scheme 3).
be observed (Table 2, entries 9 and 10). Depending on the
substitution grade of the internal double bond, the alcohol func- The electrolysis was carried out in an H-type divided cell (4G
tionality attacks at the less-substituted carbon of the internal glass filter) equipped with carbon fiber electrodes (see
double bond based on better stabilisation of the cationic inter- Supporting Information File 1). Each chamber was charged
mediate. The triple methyl-substituted starting material 2m gave with 2,6-lutidine and TBABF4 in CH3CN (0.3 M) and addition-
a 1:1 mixture of tetrahydrofuran and pyran products 3m and ally the 1,4-dienol and sodium iodide were placed in the anode
4m, the latter product is formed via a 6-endo-tet-type cyclisa- chamber. The reaction was performed at constant current elec-
tion, in an excellent combined yield of 93%. When the mixture trolysis (10 mA) at 0 °C. It is considerable that the presence of
of the 1,4-dienols (2n and 2o) was applied, the major regioi- 2,6-lutidine is crucial for a successful reaction. In the absence of
somer 2n gave the pyran exclusively in good yields, while the 2,6-lutidine only traces of the product can be observed and oxi-
minor 1,4-dienol 2o resulted in the formation of two tetrahydro- dation of the alcohol functionality takes place. It is mentionable
furan diastereomers which could be separated easily by column that under the reaction conditions no aromatic iodination could
chromatography (Table 2, entry 10). Using higher substituted be observed. Next to sodium iodide other iodide sources such as
Scheme 3: Electrochemical iodoalkoxylation of 2.
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Beilstein J. Org. Chem. 2015, 11, 174–183.
KI, I2 or Bu4NI can be used, whereas applying other halogen- electron-rich 1,4-dienols (2g and 2h) gave higher yields than in
ides such as NaBr, Et4NBr or Bu4NCl led to a complex mixture the selenoalkoxylation (Table 3, entries 7 and 8). For com-
of products.
pound 5g the structure could be verified by X-ray analysis (see
Supporting Information File 1). It is also considerable that the
In this series of experiments we focussed our attention on the 1,4-dienols 2c, 2e and 2i which did not gave the selenoether 3
aryl-substituted 1,4-dienes to avoid undesired mixtures of led to a product formation in at least moderate yields of 40% to
tetrahydrofuran and pyran derivatives as obtained in the selen- 46% (Table 3, entries 3, 5 and 9).
oalkoxylation for alkyl-substituted dienols. The results of the
electrochemical iodoalkoxylation reactions are summarised in The products of the selenoalkoxylation as well as of the
Table 3.
iodoalkoxylation are interesting building blocks for further
transformations which are under current investigation.
The electrochemical iodoalkoxylation of the aryl-substituted
1,4-dienols 2 led to the formation of the tetrahydrofuran deriva- Conclusion
tives 5 as single regio- and diastereomers. 1,4-Dienols with In conclusion, we have developed the alkoxylation of 1,4-
electron-donating and electron-withdrawing substituents as well dienols by electrochemically generated selenium and iodonium
as heterocyclic compounds gave the product of type 5 in good cations. First, the synthesis of 1,4-dienols via a cobalt-catalysed
yields. It is noteworthy, that under these reaction conditions the 1,4-hydrovinylation of substituted 1,3-dienes with allyloxy-
Table 3: Electrochemical iodoalkoxylation of 1,4-dienols 2.
Entry
1
1,4-Dienol 2
Iodofuran 5
Yielda
66%
2
3
4
60%
40%
68%
5
6
46%
68%
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Beilstein J. Org. Chem. 2015, 11, 174–183.
Table 3: Electrochemical iodoalkoxylation of 1,4-dienols 2. (continued)
7
70%
8
9
67%
46%
10
11
82%
66%
aReaction conditions: H-type cell, anodic chamber: 1,4-dienol (0.5 mmol, 1.0 equiv), NaI (1.1 equiv), 2,6-lutidine (2.0 equiv), TBABF4/CH3CN (0.3 M,
10 mL); cathode chamber: 2,6-lutidine (2.0 equiv), TBABF4/CH3CN (0.3 M, 10 mL); 0 °C, C/C, 10 mA.
trimethylsilane or allyl alcohol has been elaborated. Those 1,4- analysis. n-Pentane was added, the mixture was filtered through
dienols have been transformed into tetrahydrofuran or pyran a short pad of silica and concentrated under reduced pressure.
derivatives by constant current electrolysis of suitable selenium The crude material was dissolved in 5 mL tetrahydrofuran,
and iodonium precursors. The reactions proceed in acceptable TBAF (1 M in THF, 1.1 equiv) was added and the mixture was
to good yields in regio- and diasterioselective fashion and stirred at 0 °C for 3 h. Upon completion of the reaction 15 mL
tolerate a range of functionalities.
water were added, the mixture was extracted with diethyl ether
(three times 15 mL), dried over Na2SO4, filtered and concen-
trated under reduced pressure. The product was obtained after
column chromatography (n-pentane/diethyl ether).
Experimental
General procedure for the cobalt-catalysed
1,4-hydrovinylation of aryl-substituted buta-
1,3-dienes with allyloxytrimethylsilane and
General procedure for the cobalt-catalysed
1,4-hydrovinylation of buta-1,3-dienes with
allyl alcohol
subsequent desilylation with TBAF
Cobalt dibromo(1,3-bis(diphenylphosphino)ethane) (5 mol %),
zinc powder (10 mol %) and zinc iodide (10 mol %) were
suspended in dichloromethane and stirred at room temperature
for 20 min. Then the 1,3-butadiene (1.0 equiv) and allyl alcohol
(1.2–1.5 equiv) were added and stirred at room temperature
until complete conversion was detected by TLC and GC–MS
analysis. Pentane was added and the mixture was filtered
Cobalt dibromo(1,3-bis(diphenylphosphino)ethane)
(5–10 mol %), zinc powder (10–20 mol %) and zinc iodide
(10–20 mol %) were suspended in dichloromethane and stirred
at room temperature for 20 min. Then the 1,3-butadiene
(1.0 equiv) and the allyloxytrimethylsilane (1.2–2.0 equiv) were
added and the mixture was stirred at room temperature until
complete conversion was detected by TLC and GC–MS
181

Beilstein J. Org. Chem. 2015, 11, 174–183.
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