New strategy for production of primary alcohols from aliphatic olefins by tandem cross-metathesis/hydrogenation

Article abstract of DOI:10.1016/j.cclet.2019.10.001

Primary alcohols are widely used in industry as solvents and precursors of detergents. The classic methods for hydration of terminal alkenes always produce the Markovnikov products. Herein, we reported a reliable approach to produce primary alcohols from terminal alkenes combining with biomass-derived allyl alcohol by tandem cross-metathesis/hydrogenation. A series of primary alcohol with different chain lengths was successfully produced in high yields (ca. 90percent). Computational studies revealed that self-metathesis and hydrogenation of substrates are accessible but much slower than cross-metathesis. This new methodology represents a unique alternative to primary alcohols from terminal alkenes.

Full text of DOI:10.1016/j.cclet.2019.10.001

Journal Pre-proof
New strategy for production of primary alcohols from aliphatic olefins by
tandem cross-metathesis/hydrogenation
Ruilong Jia, Zhijun Zuo, Xu Li, Lei Liu, Jinxiang Dong
PII:
S1001-8417(19)30604-7
https://doi.org/10.1016/j.cclet.2019.10.001
CCLET 5265
DOI:
Reference:
To appear in:
Chinese Chemical Letters
Received Date:
Revised Date:
Accepted Date:
6 September 2019
19 September 2019
3 October 2019
Please cite this article as: Jia R, Zuo Z, Li X, Liu L, Dong J, New strategy for production of
primary alcohols from aliphatic olefins by tandem cross-metathesis/hydrogenation, Chinese
Chemical Letters (2019), doi: https://doi.org/10.1016/j.cclet.2019.10.001
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Communication
New strategy for production of primary alcohols from aliphatic olefins by tandem
cross-metathesis/hydrogenation
c,1
a,
a,
a,d
Ruilong Jiaa,b,1, Zhijun Zuo , Xu Li Lei Liu , Jinxiang Dong

a College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China
b Shanxi University of Traditional Chinese Medicine, Jinzhong 030619, China
c Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, China
d School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, China
 Corresponding author.
E-mail address: liulei@tyut.edu.cn (L. Liu).
1 These authors contributed equally to this work
ARTICLE INFO
Article history:
Received 6 September 2019
Received in revised form 19 September 2019
Accepted 24 September 2019
Available online
Graphical Abstract
Aliphatic olefins
H2O
H-GII
PtO2
Primary alcohols
90% yield
Tandem cross-metathesis/hydrogenation
A new synthetic methodology to produce primary alcohols by tandem cross-metathesis/hydrogenation from terminal aliphatic
olefins and biomass-derived allyl alcohol is developed.
ABSTRACT
Primary alcohols are widely used in industry as solvents and precursors of detergents. The classic methods for hydration of terminal alkenes always
produce the Markovnikov products. Herein, we reported a reliable approach to produce primary alcohols from terminal alkenes combining with
biomass-derived allyl alcohol by tandem cross-metathesis/hydrogenation. A series of primary alcohol with different chain lengths was successfully
produced in high yields (ca. 90%). Computational studies revealed that self-metathesis and hydrogenation of substrates are accessible but much slower
than cross-metathesis. This new methodology represents a unique alternative to primary alcohols from terminal alkenes.
Keywords:
Primary alcohols
Aliphatic olefins
Allyl alcohol
Cross-metathesis/hydrogenation
Anti-Markovnikov regioselectivity
Primary alcohols have tremendous industrial application as solvent and precursors of chemicals [1,2]. The hydration of terminal
olefin to alcohols is an important process in both bulk and fine chemical syntheses [3,4], however, this methodology using acid
catalysts always provided the secondary alcohols for the terminal olefin because the reaction follows Markovnikov’s rule. Although
some progress, to date, has been made on the conversion of terminal olefins to primary alcohols by metal-catalyzed methods and
———

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multistep reaction [5-9], directly achieving high selectivity of primary alcohols from terminal olefins is still difficult [10,11]. For
example, Grubbs and co-workers [8] reported an effective approach for the direct synthesis of primary alcohols from aryl-substituted
terminal olefins via triple relay catalysis, however, high regioselectivity for primary alcohols was not successful with respect to
aliphatic terminal olefins.
In reality, the two-step process including hydroformylation/reduction (Fig. 1) is currently applied for the industrial production of
primary alcohols from terminal olefins [12,13]. Hydroformylation of olefins could occur at the primary, or secondary carbon atoms of
the carbon-carbon double bond, and lead to the formation of linear (n) and branched (iso) aldehydes. Moreover, isomerizaiton of the
double bond during the hydroformylation of terminal olefins also afford the increase of iso-aldehydes [14-16].
Hydroboration/oxidation sequence could also obtain hydration products with anti-Markovnikov regioselectivity (Fig. 1). However, a
stoichiometric borane reagent should be required, and the recycle of boron waste unavoidably generated from this process is difficult.
Moreover, the usage of peroxides in the oxidation step of hydroboration could raise safety concerns when the process is applied in
large-scale production [17]. Therefore, it is very necessary to develop an alternative environmental friendly approach to produce the
primary alcohols from non-activated aliphatic olefins.
catalyst
CO, H2
H
R
Hydroformylation/hydrogenation
R
OH
R
O
R,2B
H
H2O2, NaOH
R,2B
OH
Hydroboration/oxidation
Our work
R
R
R
R
Grubbs catalyst/PtO2
C3H6O
R
OH
Fig. 1. Current strategies for the production of primary alcohols from terminal alkenes via hydroformylation/hydrogenation and
hydroboration/oxidation sequence.
Olefin cross-metathesis (CM) has now been an effective route toward the elaboration of olefinic substrates with the advent of well-
defined catalysts [18-21]. Glycerol as a byproduct accounting for 10 wt% of the total biodiesel is abundantly generated in the
production of biodiesel, and now the serious surplus of glycerol leads to the price decrease [22,23]. The non-catalytic
deoxydehydration of glycerol with formic acid to allyl alcohol has been known to be a promising and economically viable route [24],
and the high purity of allyl alcohol about 99.9 wt% could be successfully obtained by salting-out method in our lab [25]. Therefore,
allyl alcohol could be generated from the biomass-derived chemicals, and is suitable as an intermediate for fabrication of functional
organic molecules [26,27].
Herein, a new strategy (Fig. 1) for producing primary alcohols by using allyl alcohols as stating raw material through tandem cross-
metathesis/hydrogenation has been developed, a series of n-alcohols could be obtained in good yields, and the tandem procedure is
beneficial to enhance the selectivity toward n-alcohols.
The tandem metathesis/hydrogenation proceeded may involve many reactions, such as cross-metathesis, self-metathesis, and
hydrogenation among the substrates and intermediate products [28-30]. The first-step cross-metathesis between allyl alcohol and
terminal olefin with a high activity and selectivity is of great importance in achieving high yield primary alcohols. We firstly studied
the conversion of allyl alcohol by cross-metathesis with 1-ocetene by four olefin metathesis catalysts (Fig. S1 in Supporting
information) combining with PtO2, respectively. Starting from allyl alcohol, as shown in Table 1, the total three main products could be
observed with various proportions in the final products. Regarding the four olefin metathesis catalysts, allyl alcohol could be
completely converted by metathesis and hydrogenation, however, Grubbs I (GI) combining PtO2 have a poor yield (42%) toward the
goal product of 1-nonanol, probably resulting from that the first-step cross-metathesis of allyl alcohol with 1-octene has a low reaction
rate over GI catalyst, and more allyl alcohol were hydrogenated to n-propanol over PtO2 catalyst in the presence of H2 atmosphere.
Hoveyda-Grubbs II (H-GII) catalyst shows the highest yield of 92% for 1-nonaol based on allyl alcohol, with a minor byproduct of n-
propanol and 1,4-butanediol, indicating that this olefin metathesis catalyst was compatible with PtO2 hydrogenation catalyst. H-GII
catalyst was selected to combine PtO2 for the synthesis of primary alcohols in our study. The yield of 1-nonanol by tandem method is
higher than that by two-step process (entry 5 in Table 1), because metathesis is a reversible reaction, the 2-nonen-1-ol produced from
the olefin metathesis could instantaneously be consumed by hydrogenation, leading to the reaction toward the forward reaction.
Table 1 Reaction results over various olefin-metathesis for the tandem cross-metathesis/hydrogenation reaction.
HO
Grubbs catalyst
PtO2
HO
+
HO
HO
OH
Gas chromatography (GC) yield (%)
Conv.
(%)[a]
Entry
Catalyst
1,4-
n-propanol
1-nonanol
butanediol
1
2
3
4
GI/PtO2
100
100
100
100
55
11
9
<1
<1
<1
42
86
88
92
GII/PtO2
H-GI/PtO2
H-GII/PtO2
5
<1

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[b]
5
H-GII/PtO2
100
9
<1
89
Conditions: allyl alcohol (0.5 mmol), 1-octene (1.0 mmol), Ru catalyst (0.01 mmol), PtO2 (0.01 mmol) ,dichloromethane (2.5 mL), H2 (0.3
MPa), room temperature, 50 min. [a] Conversion of allyl alcohol. [b] Two step reaction: First Ru catalyst for 50min, then PtO2 for 50 min.
In fact, the tandem cross-metathesis/hydrogenation process is very complicated, the possible products obtained from allyl alcohol are
shown in Fig. 2. To further understand the reaction process, the yields for the possible products based on allyl alcohol were recorded
with various reaction times. At the initial reaction stage, the products mainly consist of 2-nonen-1-ol and 1-nonanol, with the yields of
48% and 4%, respectively, and the total of other three products (2-butene-1,4-diol, 1,4-butanediol and n-propanol) account for a very
minor proportion. The kinetic experimental data shows that the reaction rate for cross-metathesis is much faster than that of
hydrogenation. The yield of 2-nonen-1-ol is also much higher than that of the total yields of 2-butene-1,4-diol and 1,4-butanediol,
indicating that the reaction rate of cross-metathesis is larger than that for self-metathesis of allyl alcohol. The yield for the goal product
of 1-nonanol gradually increases by the continuing hydrogenation of 2-nonen-1-ol with the increase of reaction time. After 50 min, the
yield of 1-nonanol could reach a maximum accompanied with the disappearance of 2-nonen-1-ol, indicating that the cross-metathesis
of allyl alcohol with 1-octene came to an end.
2-Nonen-1-ol
HO
1-Nonanol
HO
HO
H-GII
HO
2-Butene-1,4-diol
+
OH
OH
PtO2
HO
HO
1,4-Butanediol
n-Propanol
100
90
80
70
60
50
40
30
20
10
0
2-Nonen-1-ol
1-Nonanol
2-Butene-1,4-diol
1,4-Butanediol
n-Propanol
10
20
30
40
50
60
70
Reaction time (min)
Fig. 2. Yield of products formed from allyl alcohol vs reaction time in the tandem cross-metathesis/hydrogenation
Giving that the allyl alcohol as cross-metathesis partner, we extended the substrate scope to prepare various primary alcohols under
the optimized conditions. A series of aliphatic olefins were tested as a partner with allyl alcohol, the experiment results were
summarized in Table 2. n-Alcohols in a high yield around 90% could be successfully obtained from terminal olefins, indicating that the
significant variation in chain length for terminal olefins could be tolerated. In the case of PtO2-free system, primary allyl alcohols could
also be prepared in a good yield (ca. 85%) only by cross-metathesis of allyl alcohol with terminal olefins. Primary allylic alcohols are
an important class of versatile building blocks, because they allow for a wide range of subsequent conversions, including many
possibilities for carbon-carbon bond formation reactions, and introduction of functional groups [31,32]. This tandem cross-
metathesis/hydrogenation displays excellent generality for production of primary alcohols in a good yield. Compared to the two
indirect routes for primary alcohols from terminal olefins, including hydroformylation/reduction and hydroboration/oxidation, this
tandem strategy shows much more superiority owing to the mild reaction condition and high yield for goal products, moreover, the
used allyl alcohol as a partner could be obtained from bio-mass raw materials [24].
Table 2 Scope of H-GII and PtO2 catalyzed tandem cross-metathesis/hydrogenation reaction sequence.
R
OH
t
s
y
l
a
t
a
c
s
b
Primary allylic alcohols
b
u
r
G
OH
+
R
P
tO2
G
r
u
b
b
s
c
a
t
a
l
y
s
t
R
OH
Primary alcohols
Entry
1
Substrate
CM (GC yield%)[a]
(90)
CM/Hydrogenation (GC yield%)[b]
(93)
(92)
2
3
4
(89)
(87)
(90)
(85)
(90)

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5
6
(89)
(84)
(82)
(86)
[a] Reaction conditions for CM: allyl alcohol (0.5 mmol, 1.0 equiv.), aliphatic olefins (1.0 mmol, 2 equiv.), H-GII (2 mol%, 0.02 equiv.),
dichloromethane (2.5 mL), H2 (0.3 MPa), room temperature, 50 min. [b] CM/Hydrogenation condition is identical to the CM besides the
introduction of PtO2 (2 mol%, 0.02 equiv.).
Scheme 1. Possible pathways for cross-metathesis of allyl alcohol with 1-octene.
To further understand the tandem cross-metathesis/hydrogenation reaction of allyl alcohol with aliphatic olefins, the reaction process
has been studied by using DFT calculaitons with VASP [33-35]. There are two possible pathways to prepare primary allylic alcohols
by cross-metathesis (Scheme 1). In pathway A, a vinylcarbene II is first formed from the reaction of methylidene I with allyl alcohol,
then the vinylcarbene II reacts with the 1-octene to form 2-nonen-1-ol. For the pathway B, alkylidene III is formed from the reaction of
methylidene I with 1-octene, then alkylidene III reacts with the allyl alcohol to form 2-nonen-1-ol.
As show in Scheme 2, the corresponding energy barriers of the most favorable pathways for the cross-metathesis of allyl alcohol-
first and 1-octene-first have similar energy barriers based on the methylidene complex. The ring-opening of metallacycle forming
vinylcarbene and ethylene has the highest energy barriers of allyl alcohol-first and 1-octene-first, wherever the corresponding energy
barriers are 0.52 eV and 0.54 eV, respectively. In the case of H-GII, the highest energy barrier of allyl alcohol-first and 1-octene-first
are 0.59 eV and 0.55 eV, respectively (Figs. S5 and S6 in Supporting information). The results show that both allyl alcohol-first and 1-
octene-first are possible for allyl alcohol and 1-octene cross-metathesis whatever the model of catalyst is methylidene complex or H-
GII. The reaction pathways of allyl alcohol and 1-octene cross-metathesis are different from that for diene and alkene cross-metathesis,
which Grubbs and co-workers find that the pathway of diene-first is more easily than that of alkene-first [36].
Considering that self-metathesis of substrates have a significant effect on the final products, the allyl alcohol self-metathesis and 1-
octene self-metathesis have been investigated by means of DFT calculations. The energy barrier for the reaction of vinylcarbene 5 with
allyl alcohol is 0.72 eV (Fig. S7 in Supporting information), which is much higher than that of vinylcarbene 5 with 1-octene (0.26 eV).
Similarity, the energy barrier for the reaction of vinylcarbene 12 with 1- octene is 0.66 eV (Fig. S8 in Supporting information), which
is also well above that of vinylcarbene 12 with allyl alcohol (0.15 eV). The result demonstrates that the cross-metathesis of 1-octene
with allyl alcohol occurs more easily than the self-metathesis of the substrates, which is similar with the calculated results of diene and
alkene cross-metathesis [36].
Finally, hydrogenation of allyl alcohol and 1-octene (Figs. S9 and S10 in Supporting information) over the Pt(100) surface are
studied. The highest energy barriers for the formation of n-propanol and n-octane corresponding to allyl alcohol and 1-octene
hydrogenation are 0.90 eV and 0.88 eV, respectively, which is much higher than that of allyl alcohol and 1-octene cross-metathesis
(0.52 eV). The calculation result also indicates that the hydrogenation rate of allyl alcohol and 1-octene are much slower than that for
allyl alcohol and 1-octene cross-metathesis, which is in good agreement with our experimental results.
In conclusion, we have developed a new synthetic methodology to produce primary alcohols by tandem cross-
metathesis/hydrogenation of allyl alcohol with terminal aliphatic olefins. The experimental and DFT theoretical results suggest that
hydrogenation rate of olefin substrates are much slower than olefin metathesis, and the cross-metathesis of substrates has an
overwhelming advantage over self-metathesis. Compared to the classic hydroformylation/reduction and hydroboration/oxidation
routes, our strategy allows for the reaction can proceed in a more mild condition to obtain primary alcohols in high yields and excellent
selectivity from aliphatic olefins, thus rendering this methodology attractive for industrial applications.

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Scheme 2. Most favorable pathways for the cross-metathesis of allyl alcohol-first (A) and 1-octene-first (B) (unit: eV). Olefin π-complexe
have been omitted in the scheme. Letters a and b refer to conformational changes of the chlorine ligand.
Declaration of interests
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence
the work reported in this paper.
The authors declare the following financial interests/personal relationships which may be considered as potential
competing interests:
Acknowledgment
This work was financially supported by the National Natural Science Foundation of China (Nos. 21322608 and 21276174), the Natural
Science Foundation of Shanxi Province (No. 201801D121055), and Program for the Shanxi Young Sanjin Scholar.

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