(E)-Specific direct Julia-olefination of aryl alcohols without extra reducing agents promoted by bases

Article abstract of DOI:10.1039/c5cc01965f

An unprecedented base-promoted direct olefination of aryl alcohols with sulfones via a Julia-type reaction has been described. No extra reductants are needed for Julia reaction since alcohols work as double sources of aldehydes and the hydride. Generally high yields were given for both terminal and highly (E)-selective internal olefins.

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(E)-Specific Direct Julia-Olefination of Aryl Alcohols
without Extra Reducing Agents Promoted by Bases
Cite this: DOI: 10.1039/x0xx00000x
Chuan-Zhi Yao,† Qiang-Qiang Li,† Mei-Mei Wang, Xiao-Shan Ning, and Yan-Biao
Kang*
Received 00th January 2012,
Accepted 00th January 2012
DOI: 10.1039/x0xx00000x
www.rsc.org/
2a, thus 0.5 equiv of NaH gave rise to a dramatic drop of the
conversion from 87% to 33% (Entry 9). Dimethyl sulfone 2b afforded
a slightly lower conversion compared to that of 2a (Entry 12), while
Wittig reagent 2c gave only 28% conversion (Entry 13). The reaction
under air atmosphere resulted in a slight drop of conversion (Entry
14). Thus the conditions described in entry 10 was chosen as the
standard conditions.
An unprecedented base promoted direct olefination of aryl
alcohols with sulfones via a Julia-type reaction has been
described. No extra reductants are needed for Julia reaction
since alcohols work as double sources of aldehydes and the
hydride. Generally high yields were given for both terminal
and highly (E)-selective internal olefins.
The Olefination is one of the most important C=C bond formation
reactions1 since olefins are very important feedstocks or intermediates
in both industry and laboratory. Despite numerous methods have been
developed to construct C=C bonds, the olefination of carbonyl
compounds, such as Wittig reaction;2-3 Horner-Wadaworth-Emmons
reaction,4 Peterson olefination,5 Julia olefination (Scheme 1, top),6
Tebbe olefination,7 dominates the main approaches of olefination in
organic synthesis. Recently, the olefination of alcohols via a Wittig-
type reaction of in situ generated carbonyl compounds has been
accomplished by the one-pot oxidation-olefination process catalyzed
by palladium-rhodium, copper, ruthenium, or nickel.8 Nevertheless,
the direct olefination of alcohols via either Julia-type or Wittig-type
reaction have been barely reported. Until near recently, Milstein and
co-workers first reported a powerful method of one-step strategy for
the olefination of alcohols with sulfones catalyzed by pincer PNN
ruthenium complexes.9 In that work, various aryl methanols could
give the terminal alkenes in moderate yields (Scheme 1, middle).
Bases such as tBuOK and NaH proved sometimes to be crucial in
either metal-free or metal catalyzed oxidative-reductive coupling of
alcohols and coupling reactions.10-12 During the course of our work on
the base promoted direct amination of alcohols via a self-hydride
transferring strategy, it was found that in the presence of bases such
as NaH or tBuONa, the reaction of benzyl alcohol 1a and phenyl
methyl sulfone 2a could afford styrene in high yields (Scheme 1,
bottom). In this work, the branched side-products13 such as 1-methyl
styrenes were not observed. Various bases were then investigated
(Table 1). Without base there was no conversion of 1a (Entry 1). The
bases such as tBuONa, tBuOK, NaH and KOH gave higher
conversions. Excess base is necessary for the deprotonation of sulfone
Scheme 1
.
Next, various alcohols were investigated to test the scope of this
method. Aryl methanols reacted with PhSO2Me 2a in the presence of
NaH and the desired olefins were afforded without side-products.
Excess 1a could be recycled in 90%. For terminal olefins listed in
Table 2, generally high isolated yields were given after careful
purification on silica gel column despite the styrene products are
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normally volatile. For example, styrene 3a was achieved in 87% yield. 5a was proposed. Despite intermediates 9 and 10 have not been
The olefin bearing a heterocylcle such as 3b was obtained in 84% observed in the reaction yet,16 the treatments of 9 and 10 under
yield. Other substituents such as methoxyl (3d and 3f), reaction conditions could give styrene 3a in good to high yields
trifluoromethyl (3i), bromo (3j), or other groups on phenyl groups (Scheme 3, Eqs 4 and 5).17 Key intermediate 5a might regenerate via
were all tolerable under the reaction conditions.
hydride transferring reduce of 9 by 1a.18
For the internal olefins, the standard reaction conditions were
employed with phenyl alkyl sulfones 2d-2f instead of 2a (Table 3).
Various aryl methanols and sulfones were investigated and the
corresponding internal olefins 4 were isolated in generally good to
high yields. The olefination is highly E/Z-selective and in all cases
only (E)-isomers were obtained. When PhSO2CH2Ph 2d was
subjected to the reaction conditions with benzyl alcohol 1a, trans-
stilbene 4a was isolated in 90% yield. Other substituted stilbenes (4b
and 4c) or styryl heterocycles (4d and 4e) could be achieved from 2d
in high yields as well. The direct olefination of cinnamic alcohol with
2d afforded diene 4g in 58% yield. PhSO2Et 2e and PhSO2CH2Py 2f
gave corresponding internal (E)-olefins 4i, 4h-l in good to high yields.
Table 2. Terminal Olefins Direct from Alcoholsa
Table 1. Screening Reaction Conditionsa
Entry
1
2
3
4
5
6
7
8
Base(equiv)
—
2
T/°C
130
130
130
130
130
130
130
130
130
130
135
135
135
135
t/h
24
24
24
24
24
24
24
24
24
24
5
3a(%)b
0
70
78
71
40
68
30
10
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2b
2c
2a
tBuONa (1.5)
NaH (1.5)
tBuOK (1.5)
MeONa (1.5)
KOH (1.5)
nBuLi (1.5)
LiHMDS (1.5)
NaH (0.5)
NaH (1.0)
NaH (2.5)
NaH (2.5)
NaH (2.5)
NaH (2.5)
9
33
10
11
12
13
14d
71
87c
71
a Conditions: 2a (1 mmol), 1 (1 mL), NaH (2.5 mmol), 135 °C, argon, isolated
yield. The excess alcohols could be recylcled quantatively (see Supporting
Information for details).
5
5
5
28
75
a
Conditions: 1a (1 mL), 2 (1 mmol), base (0.5-2.5 mmol), 130 or 135 °C,
argon. All bases and solvents were tested by ICP-AES for trace transition
metals (e.g., Ru, Rh, Ir, Pd, Pt, Cu, Fe: not detected in NaH or reaction
mixture). See Supporting Information. b Determined by 1H NMR (400 MHz)
Table 3. Internal Olefins Direct from Alcohola
c
using 1,4-dioxane and DMSO as internal standards. Excess starting mterial
1a was recovered quantatively. d Under air (PhCHO: 0.04 mmol after reaction).
The effects of the amount of base (NaH) and sulfone (PhSO2Me)
were investigated kinetically. The homogeneous reaction solution was
1
monitored by H NMR under standard reaction conditions. A linear
dependence of the initial rate on the amount of NaH was observed
(Fig. 1A), while that was a zeroth dependence on the amount
PhSO2Me (Fig. 1B). The deuterium labeling experiment demonstrated
a first order KIE, indicating a rate-determining step of the C-H bond
cleavage (Scheme 2).
A possible mechanism was proposed in Scheme 4. First, trace
benzaldehyde 5a formed via a thermal dehydrogenation of 1a
(Scheme 3, Eq. 1),14 followed by the addition of sulfone salt 2a-Na to
form intermediate 6a-Na. Sulfone alcohol 6a could be isolated and
was treated either in the presence or absence of alcohol 1a,15 but only
the reaction with 1a gave 91% of olefin 3a (Scheme 3, Eq. 2),
indicating that alcohol 1a is necessary for liberating olefin 3a. Mainly
PhSO2Na 7 was observed in the immediate 1H NMR test of the
reaction mixture, while after work-up, both 7 and PhSO3Na 8 could
be isolated. The treatment of 8 with 1a under olefination conditions
gave no 7, while the exposure of 7 in air resulted the oxidation of 7 to
8, indicating that sodium benzenesulfinate 7 is the final form of
sulfone 2a. Thus a reaction cycle including 6a-Na, 6a'-Na, 9, 10, and
a
Conditions: 2d-f (1 mmol), 1 (1 mL), NaH (2.5 mmol), 135 °C, argon,
isolated yield. The excess alcohols could be recylcled quantatively (see
Supporting Information for details).
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Conclusions
6
5
4
3
2
1
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
In conclusion, a base promoted direct olefination of aryl alcohols
with sulfones via a Julia-type reaction has been established. This
transition metal free process avoids the side reactions such as
dehydrogenative oxidation of alcohols, formation of branched
styrenes and hydrogenation of olefin products by liberated hydrogen.
High (E)-selectivity provides a highly efficient access to internal (E)-
olefins. Non-toxic process, simple reaction conditions, the cheap base
reagents, as well as the recycling and reuse of sulfinate waste are all
the highlights of this method.
(B)
(A)
1.75
2.00
2.25
2.50
0.8
1.0
1.2
1.4
NaH (equiv)
PhSO2Me (equiv)
Figure 1. Dependence of the initial rate on (A) NaH and (B) PhSO2Me.
Notes and references
a Center of Advanced Nanocatalysis (CAN) and Department of Chemistry,
University of Science and Technology of China, Hefei, Anhui 230026,
China
Scheme 2. Kinetic Isotope Effects.
E-mail: ybkang@ustc.edu.cn
†
C.Z.Yao and Q.Q.Li contributed equally to this work.
Electronic Supplementary Information (ESI) available: Experimental
details and spectroscopic data for all products. See
DOI: 10.1039/c000000x/
Acknowledgements
We thank the National Natural Science Foundation of China (NSFC
21404096, U1463202), the Fundamental Research Funds for the Central
Universities of China (WK2060190022, WK2060190026), and USTC for
financial support.
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