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Hetero diacylation of 1, 1-diborylalkanes: Practical synthesis of 1, 3-diketones
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Liang-Hua Zoua, *, Min Fana, b, Lu Wangb, *, Chao Liub, *
Chinese Chemical Letters | 2020, 31(7) : 1911 - 1913
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Chinese Chemical Letters | 2020, 31(7): 1911-1913
• Communication •
Hetero diacylation of 1, 1-diborylalkanes: Practical synthesis of 1, 3-diketones
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Liang-Hua Zoua, *, Min Fana, b, Lu Wangb, *, Chao Liub, *
Affiliations
  • a Key Laboratory of Carbohydrate Chemistry and Biotechnology, Ministry of Education, School of Pharmaceutical Sciences, Jiangnan University, Wuxi 214122, China
  • b State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute of LICP, Lanzhou Institute of Chemical Physics(LICP), Chinese Academy of Sciences, Lanzhou 730000, China
Published: 2020-07-15 doi: 10.1016/j.cclet.2019.12.016
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An efficient protocol for the synthesis of asymmetric 1, 3-diketones was reported through diacylation of 1, 1-diborylalkanes using two different acyl sources. In this transformation, an enolate boron species was initially formed by introducing an acyl group, then it was trapped by another acyl group to form 1, 3-diketone. This method not only provided the gateway to obtain a series of 1, 3-diketones, but also afforded an operationally simple and efficient access to pyrazoles and isoxazoles.

1, 1-Diborylalkanes  /  Diacylation  /  Enolate boron species  /  Boron-stabilized carbanion intermediates  /  1, 3-Diketones
Liang-Hua Zou, Min Fan, Lu Wang, Chao Liu. Hetero diacylation of 1, 1-diborylalkanes: Practical synthesis of 1, 3-diketones[J]. Chinese Chemical Letters, 2020 , 31 (7) : 1911 -1913 . DOI: 10.1016/j.cclet.2019.12.016
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Many natural products containing 1, 3-diketone moiety exhibit broad biological activities, such as antimicrobial, antiviral, and antifungal activities [1]. They can also act as bidentate ligands in metal catalysis and luminescent materials [2, 3]. Besides, 1, 3-diketones are widely used as versatile synthons for the construction of various heterocycles [1, 4-6] or C—C bond formation [7-15]. Therefore, considerable efforts have recently been devoted to the synthesis of this useful scaffold [1, 4]. So far, several strategies have been developed for the synthesis of 1, 3-diketones, including (a) Enolate strategy (Scheme 1a) [16-22], (b) Umpolung strategy (Scheme 1b) [23-25], and (c) carbonylation of ketones (Scheme 1c) [26]. Despite these advances, there are still some important challenges, such as the requirement of multistep preparation of precursors, the use of toxic or expensive reagents, and limited substrate scope, that need to be addressed for the synthesis of 1, 3-diketones. Hence, the development of new and efficient protocols in which such challenges can be overcome are of great significance in synthetic organic chemistry.
1, 1-Diborylalkanes, as a linkage with two binding sites, have attracted increasing attention due to their significant application in mono- or difunctionalization and the fact that they can be employed as a good platform molecule for bifunctional transformation [27]. However, the difunctionalization of the two C—B bonds of 1, 1-diborylalkanes is still underdeveloped [27]. Usually, this transformation is realized through cross-coupling reactions under transition metal catalyzed conditions [28-35]. Furthermore, the 1, 1-diborylalkanes could be used in nucleophilic addition to carbonyl compounds for the synthesis of enolate boron species through the boron-stabilized carbanion intermediates. These enolate boron species acted as nucleophiles, which could be further trapped by another electrophile to build new chemical structures through the difunctionalization of 1, 1-diborylalkanes [36]. Based on this concept, our group recently first introduced carboxylic acid as an acyl synthon to form an enolate boron species, followed by trapping with various electrophiles to build ketones [37]. We reasoned that 1, 3-diketones could be formed when the enolate boron species were formed, in combination with the insertion of another acyl source. Herein, we report an efficient protocol for the synthesis of asymmetric 1, 3-diketones through diacylation of 1, 1-diborylalkanes using two different acyl sources (Scheme 1d).
In our previous report, we developed a dual functionalization of α-monoboryl carbanions through deoxygenative enolization with carboxylic acids [37], in which the α-monoboryl carbanions was formed using CH3Li to activate 1, 1-diborylalkane, followed by addition to carboxylic acids, and then a new enolate boron specie was formed and trapped by another acyl source to afford 1, 3-diketones. In this report, the substrate scope was extensively explored under the optimized reaction conditions. In the meanwhile, the application of 1, 3-diketones was investigated to synthesize poly-substituted pyrazoles and isoxazoles. Firstly, in order to explore the generality of the reaction, a broad range of aromatic acyl chlorides were investigated under the optimized conditions and the results are summarized in Scheme 2. At first, product 3aa was obtained in 74% yield. Substrates bearing electron-donating groups –Me and –OMe were also successfully employed in the reaction, providing the corresponding products 3ab and 3ac in 62% and 59% yields, respectively. For the substrates containing electron-withdrawing group –CF3, and halogen –F, and –Br, the reaction also afforded products 3ad-3af in good yields (52%, 59% and 54% yields, respectively). Next, the reaction was turned to other substrates with substituents ortho-Cl and meta-Br affording products 3ag and 3ah in 62% and 64% yields, respectively. Furthermore, the substrate bearing 2-naphthyl group also reacted well under the standard conditions, affording product 3ai in 68% yield. Two heterocycle acyl chlorides were further investigated in the reaction, producing products 3aj and 3ak in 63% and 52% yields, respectively.
In order to further explore the scope of the reaction, a series of carboxylic acids were investigated and the results are summarized in Scheme 3. Functional groups, such as p-Me, p-OMe, p-NMe2 and p-F, were well tolerated, providing the corresponding products 3al- 3ao in good yields. Furthermore, the substrate bearing naphthyl group was also successfully employed in the reaction, affording product 3ap in 78% yield. Next, several other 1, 1-diborylalkanes were then tested. These 1, 1-diborylalkanes were easily accessed by our development on the gem-diborylation of aldehydes, ketones and carboxylic esters [38-40]. Benzoic acid was applied as the coupling partner, and 4-fluorobenzoyl chloride was used as the electrophilic trapping reagents to demonstrate the advantage of this method for the synthesis of various α-substituted 1, 3-diketones. These alkyl and benzyl substituted 1, 1-diborylalkanes were suitable for this transformation, affording the desired products in moderate to good yields (3aq, 3ar, 3as)
Having successfully developed an efficient method for the preparation of 1, 3-diketones, we turned our focus on the utility of these compounds to access heterocyclic scaffolds [35, 41-43]. A series of 1, 3-diketones were reacted with hydrazine hydrate to produce trisubstituted pyrazoles and the results are summarized in Scheme 4. Generally, almost all the tested examples provided the corresponding products 4aa-4ah in excellent yields. According to literature report, fast tautomerism of the 1H-pyrazoles generally occurred in CDCl3 solution [44-46]. Therefore, no isomers were observed for those products and those products were presented in one form. Furthermore, phenylhydrazine was also successfully employed to react with 3aa, affording terasubstituted pyrazole 5aa in 78% yield (Scheme 5a). In the meanwhile, condensation of 3aa with hydroxylamine led to the formation of the corresponding isoxazole 6aa in 89% yield in the presence of iodine (Scheme 5b). In conclusion, we developed a new method to synthesize various 1, 3-diketones via the cross-coupling of 1, 1-diborylalkanes and two different acyl sources.
In the process, the inert carboxylic acids could be directly transformed to 1, 3-diketones and many functional groups were well tolerated. Furthermore, these 1, 3-diketones have been successfully employed to construct pyrazoles and isoxazoles. Ongoing research, including further mechanistic details and expanding the substrate scope, are currently underway.
Declaration of competing interest
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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.
Acknowledgments
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This work was supported by the National Natural Science Foundation of China (Nos. 91745110, 21673261, 21603245, 21703265, 21872156, 21802150, 21773210 and 21603190), Natural Science Foundation of Jiangsu Province (Nos. BK20190002, BK20181194 and BK20180247). Support from the Young Elite Scientist Sponsorship Program by CAST (No. YESS20170217), the Youth Innovation Promotion Association CAS (No. 2018458) was also acknowledged.
Appendix A. Supplementary data
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Supplementary material related to this article canbefound, in the online version, at doi: https://doi.org/10.1016/j.cclet.2019.12.016.
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Year 2020 volume 31 Issue 7
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Article Info
doi: 10.1016/j.cclet.2019.12.016
  • Receive Date：2019-10-22
  • Online Date：2026-01-31
  • Published：2020-07-15
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  • Received：2019-10-22
  • Revised：2019-11-25
  • Accepted：2019-12-09
Affiliations
    a Key Laboratory of Carbohydrate Chemistry and Biotechnology, Ministry of Education, School of Pharmaceutical Sciences, Jiangnan University, Wuxi 214122, China
    b State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute of LICP, Lanzhou Institute of Chemical Physics(LICP), Chinese Academy of Sciences, Lanzhou 730000, China
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表12种不同金属材料的力学参数
科
Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
total species (%)		 属
Genus		 种数
Number of
species		 占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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