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DOI: 10.1055/a-2589-4376
Ruthenium-Catalyzed Isomerization/(Transfer) Hydrogenation of Allylic Alcohols
This work was supported by the National Natural Science Foundation of China (22071242 and 21871260), the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB20000000), and the Fujian Natural Science Foundation (2021J01522).
Abstract
Allylic alcohols, renowned for their reactivity in epoxidation, dihydroxylation, allylic substitution, and isomerization, stand as pivotal intermediates in organic synthesis. While numerous reviews have delved into the above transformations of allylic alcohols, a significant void remains in the comprehensive discussion of their conversion into saturated alcohols under (transfer) hydrogenation conditions. This short review endeavors to fill that void by highlighting the tandem isomerization/(transfer) hydrogenation of allylic alcohols facilitated by ruthenium catalysts. We hope that this account will advance the understanding and application of allylic alcohols in (transfer) hydrogenation, fostering innovation and discovery in this critical area.
1 Introduction
2 Ruthenium-Catalyzed Conversion of Allylic Alcohols into Saturated Alcohols under Transfer Hydrogenation Conditions
3 Ruthenium-Catalyzed Conversion of Allylic Alcohols into Saturated Alcohols under Hydrogenation Conditions
4 Conclusion
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Key words
allylic alcohol - hydrogenation - transfer hydrogenation - redox isomerization - ruthenium catalystIntroduction
Allylic alcohols are prevalent in many natural sources and are important intermediates in both industrial and academic settings.[1] One significant transformation involving allylic alcohols is their catalytic isomerization into carbonyl compounds, which is highly valued in synthesis due to its redox-neutral and atom-economic nature. This transformation has garnered considerable attention and has been the subject of numerous reviews.[2] Various transition metals have demonstrated catalytic activity in the redox isomerization of different allylic alcohols. Additionally, these transition metals are also widely used for the reduction of carbonyl groups, either through direct hydrogenation with hydrogen gas (H2) or by transfer hydrogenation.[3] Ruthenium is also an effective catalyst for hydrogen transfer, enabling the conversion of lower alcohols into higher alcohols.[4]
Considering these points, it is plausible to hypothesize that a Ru catalyst, in conjunction with a suitable hydrogen source, could facilitate reduction of the C=C bond in allylic alcohols through a two-step tandem process (Scheme [1a]). The first step involves the redox isomerization of the allylic alcohol to a carbonyl intermediate. The mechanisms of redox isomerization reactions can be classified into two types: (i) a mechanism involving a metal alkoxide, and (ii) base-facilitated formal 1,3-hydrogen transfer. Subsequently, the resulting carbonyl group undergoes hydrogenation. This overall transformation presents an attractive alternative to traditional transition-metal-catalyzed direct C=C hydrogenations. It is noteworthy that the most commonly used catalysts for the direct hydrogenation of allylic alcohols are those used for the hydrogenation of non-functionalized olefins, such as Ir complexes (Scheme [1b]).[5] There are relatively few reports on Ru- or Rh-catalyzed direct hydrogenation of allylic alcohols, since these catalysts usually require a coordinating functional group and the hydroxy group does not serve as a typical coordinating group.[6] In addition, the reaction conditions also have an important impact on the choice between the two mechanisms. For the reaction catalyzed by Ru, the conversion of allylic alcohols into saturated alcohols mostly proceeds through the tandem isomerization/(transfer) hydrogenation under basic conditions, whereas under neutral conditions, the C=C double bonds are hydrogenated directly. In this short review, we summarize the developments in Ru-catalyzed isomerization/(transfer) hydrogenation of allylic alcohols. We aim to underscore the practical applications of these reactions, broadening the horizons of hydrogenation and contributing to advancements in novel materials and technological innovations.
# 2
Ruthenium-Catalyzed Conversion of Allylic Alcohols into Saturated Alcohols under Transfer Hydrogenation Conditions
In 2007, Cadierno, Gimeno and co-workers[7] introduced a highly efficient technique for selectively reducing the C=C bond in allylic alcohols (Scheme [2]). This method relied on a unique Ru-catalyzed process that combined redox isomerization of an allylic alcohol with transfer hydrogenation. The reactivity in i PrOH significantly decreases as the number of substituents on the C=C bond within the substrates increases, which is a tendency commonly observed in catalytic redox-isomerization reactions. For monosubstituted allylic alcohols, the reduction can achieve nearly quantitative yields, even with low ruthenium loadings (Scheme [2, 2a–h]). However, for di- and trisubstituted allylic alcohols, higher ruthenium concentrations are required (Scheme [2, 2j,k,m–p]), with an exception for those containing a less bulky methyl group (Scheme [2, 2i,l]). An interesting aspect is that, despite the insolubility of the catalyst in water, reduction of the substrates could still be carried out efficiently in an aqueous environment (Scheme [3]). The rate of the overall process in water was not determined by the degree of substitution on the C=C bond (Scheme [3, 2a–p]). In contrast, those reactions involving primary alcohols proceeded faster than the others (Scheme [3, 2b,l–m]). Monitoring the product distributions revealed that the rate-limiting step is transfer hydrogenation rather than isomerization. This finding provides valuable insights into the mechanism of the reaction.
In 2010, Williams et al.[8] employed 1,4-butanediol as the reducing agent in their study to achieve a sequence of isomerization and reduction using various unsaturated alcohols (Schemes 4 and 5). The unique characteristic of 1,4-butanediol lies in its essentially irreversible nature due to the formation of a butyrolactone during the reaction. This property negates the need to use it in large excesses to complete the reduction process. The authors utilized a catalyst system comprising [Ru(p-cymene)Cl2]2 in conjunction with dppf, which proved highly effective for this transformation. A range of allylic alcohols was successfully converted into the corresponding saturated alcohols with excellent yields (Scheme [4]). When geraniol was used, only the alkene group within the allylic alcohol moiety underwent reduction (Scheme [4, 2p]). A homoallylic alcohol also underwent reduction to give the product 2s in 91% yield (Scheme [5a]). Additionally, in the case of a propargylic alcohol, the reduction resulted in a mixture of the saturated alcohol and cinnamyl alcohol with a ratio of 76:24 (Scheme [5b]).
In 2011, Cadierno, Crochet and Díaz-Álvarez[9] found that both pharmaceutical (Pharma.) and technical (Tech.) grades of glycerol, renowned for its biodegradability and negligible toxicity, could serve as the solvent and hydrogen source in the ruthenium-catalyzed reduction of allylic alcohols. Of the multiple Ru-based catalysts examined, [RuCl2(η 6-C6H6)(DAPTA)] (C3 ), paired with KOH, stood out as the most effective, yielding substantial quantities of the target saturated alcohols 2a,t–v (Scheme [6]). It is worth emphasizing that, after a straightforward extraction of the reduced alcohol with diethyl ether, the glycerolic phase containing C3 retained its reactivity and could be recycled effectively for a minimum of four consecutive reactions, showcasing its potential for sustainable and economical practice.
In 2012, Sowa Jr. et al.[10] reported the first asymmetric transfer hydrogenation of allylic alcohols (Scheme [7a]). This process achieved high yields and remarkable enantioselectivities (Scheme [7a, ] 2p,w,x). Screening of the catalyst revealed that apart from an in situ prepared Ru complex, the commercially available [{(S)-tol-binap}RuCl2(p-cymene)] catalyst C4 was also highly effective for catalyzing the asymmetric transfer hydrogenation of allylic alcohols. To further understand the reaction mechanism, the authors conducted deuterium-labeling experiments. These experiments provided insights into the enantioselective isomerization/transfer hydrogenation process (Scheme [7b]). Specifically, they found that allylic isomerization played a crucial role in the asymmetric induction step. This step was responsible for the excellent selectivity observed for allylic alcohols, as well as the lower selectivity for other unsaturated substrates.
Cahard, Renaud and co-workers[11] have reported the tandem isomerization/transfer hydrogenations of γ-CF3 allylic alcohols (Scheme [8]). This process efficiently produced saturated alcohols in high yields (Scheme [8, 4a–k]). Notably, the technique was applicable for synthesizing trifluoromethylated citronellol 4k. By utilizing 19F NMR spectroscopy to monitor the reaction, it was unequivocally demonstrated that a saturated ketone arising from the isomerization step serves as an intermediate within this tandem process.
In 2014, Adolfsson et al.[12] introduced a one-pot method for converting racemic allylic alcohols directly into enantiomerically enriched saturated alcohols (Scheme [9]). This tandem isomerization/asymmetric transfer hydrogenation reaction was catalyzed effectively by a combination of [{Ru(p-cymene)Cl2}2] C2 and the α-amino acid hydroxyamide ligand L2 . The reaction occurred under mild conditions using a mixture of EtOH and THF as the solvent. The resulting saturated alcohols were isolated in yields ranging from good to excellent and exhibited enantiomeric excesses as high as 93% (Scheme [9, 2d–f,h,j,k]). This method complements earlier approaches developed by Sowa Jr.,[10] as it can be applied to both primary and secondary allylic alcohols.
In 2015, following up their earlier research on converting primary allylic alcohols into enantiomerically pure primary alcohols, Sowa Jr. et al.[13] introduced another technique for the enantioselective synthesis of chiral secondary alcohols from racemic secondary allylic alcohols (Scheme [10, 2e,q,y,z]). Unlike the previous enantioselective isomerization/transfer hydrogenation sequence, this new method required a distinct isomerization/asymmetric transfer hydrogenation process, which was also validated by Adolfsson and colleagues.[12] To enhance the enantioselectivity, the authors employed a carefully programmed temperature profile, which initially involved equilibrating the precatalyst with (S,S)-TsDPEN at 80 °C, subsequently introducing the premixed substrate and base at a reduced temperature of 45 °C, and finally allowing the reaction to proceed at 25 °C.
Recently, Fang et al.[14] achieved a Ru-catalyzed formal asymmetric reductive isomerization of α-hydroxyenones. This study unveils a mechanism that combines base-facilitated α-hydroxyenone isomerization with Ru-catalyzed asymmetric transfer hydrogenation. Through this process, a variety of α-hydroxyenones featuring disubstituted olefin units can be efficiently converted into the desired acyloins (Scheme [11, 6a–e]). They also explored the reactivity of trisubstituted enones. Notably, substrates with α′-substituents were found to be unreactive under standard conditions. In contrast, substrates featuring β′-substituted units reacted smoothly to produce the desired products with high enantiomeric excesses (Scheme [11, 8a–d]). This indicates that the position of the substituent on the enone plays a crucial role in determining the reactivity of the reaction. Furthermore, the authors tested a range of substrates containing conjugated diene units. These substrates were also found to be suitable for the reaction, and the transformation involving the diene moiety exhibited high regioselectivity with one of the alkene units remaining untouched (Scheme [12, 10a–h]). Detailed mechanistic studies were also conducted to uncover the mechanism of the isomerization process, providing insights into how the base and ruthenium catalyst work together to facilitate the desired transformation (Scheme [13]).
# 3
Ruthenium-Catalyzed Conversion of Allylic Alcohols into Saturated Alcohols under Hydrogenation Conditions
In 2019, Ohkuma et al.[15] made a development by converting racemic β-ylidenecycloalkanols into saturated cis-β-substituted cycloalkanols with remarkable enantio- and diastereoselectivities (Scheme [14, 12a–i]). For substrate 13a featuring a fused benzene ring, the product 14a was obtained with a moderate enantiomeric excess, potentially attributed to the steric hindrance involved (Scheme [15]). This conversion was achieved through a tandem process involving isomerization followed by asymmetric hydrogenation. This innovative two-step process enabled the asymmetric hydrogenation of racemic allylic alcohols with formal dynamic kinetic resolution, which was not feasible through a single-step transformation.
Mechanistic experiments suggest that the catalytic cycles involve two reversible distinct species, designated as B and F (Scheme [16]). These species are generated through the ruthenacyclic amide intermediate A. The complex B plays a crucial role in catalyzing the isomerization of allylic alcohols into racemic α-substituted ketones. The complex F then steps in to catalyze the asymmetric hydrogenation of the racemic α-substituted ketones through dynamic kinetic resolution.
Using a Ru-BIMA/DIOP-type catalyst with less steric hindrance, Wang, Tang and co-workers[16] successfully achieved the asymmetric hydrogenation of both cyclic (Scheme [17, 14a–o]) and acyclic (Scheme [18, 16a–k]) racemic secondary allylic alcohols, leading to enantiomerically enriched chiral alcohols featuring adjacent stereocenters. Notably, β-ylidenecycloalkanols containing a fused benzene ring were found to be less effective substrates in Ohkuma’s research.[15] Mechanistic investigations revealed that the isomerization step uniquely required the base t BuOK, contrasting with Ohkuma’s findings.[15] Furthermore, deuterium-labeling studies provided evidence for a t BuOK-facilitated intramolecular 1,3-hydrogen transfer mechanism during the allylic alcohol isomerization. The stereoselectivity of the resulting products is governed by chiral Ru-catalyzed hydrogenative dynamic kinetic resolution (Scheme [19]). The authors employed the Spartan model to elucidate the observed enantioselectivity and diastereoselectivity. During the reduction of ketone S-III to yield the (S,S)-alcohol product, steric hindrance is present between the phenyl group in S-III and the phenyl group on one of the phosphine atoms of the ruthenium complex. In contrast, for the reduction of ketone R-III to produce the (S,R)-alcohol product, the process is less sterically hindered and more energetically favorable.
# 4
Conclusion
Despite there being numerous reviews summarizing the isomerization of allylic alcohols and (transfer) hydrogenation of ketones, there was a lack of focus on the conversion of allylic alcohols into saturated alcohols under (transfer) hydrogenation conditions. This short review aims to fill this gap by providing a comprehensive summary of the ruthenium-catalyzed isomerization/(transfer) hydrogenation tandem process for allylic alcohols, encompassing both racemic and asymmetric conversions. By shedding light on the tandem mechanisms, we aim to stimulate further research into the reduction of allylic alcohols or other unsaturated alcohols under (transfer) hydrogenation conditions. Ultimately, it is hoped that this short review will contribute to the development of novel reaction modes and synthetic methodologies, pushing the boundaries of (transfer) hydrogenation in organic synthesis.
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Conflict of Interest
The authors declare no conflict of interest.
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Corresponding Authors
Publication History
Received: 12 March 2025
Accepted after revision: 16 April 2025
Accepted Manuscript online:
16 April 2025
Article published online:
15 May 2025
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References
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