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Transition-Metal-Catalyzed Transfer Carbonylation with HCOOH Or HCHO As Non-Gaseous C1 Source

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Transition-Metal-Catalyzed Transfer Carbonylation with HCOOH Or HCHO As Non-Gaseous C1 Source Coordination Chemistry Reviews 336 (2017) 43–53 Contents lists available at ScienceDirect Coordination Chemistry Reviews journal homepage: www.elsevier.com/locate/ccr Review Transition-metal-catalyzed transfer carbonylation with HCOOH or HCHO as non-gaseous C1 source ⇑ ⇑ Jian Cao a, , Zhan-Jiang Zheng a, Zheng Xu a, Li-Wen Xu a,b, a Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou 311121, PR China b State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, PR China article info abstract Article history: While carbon monoxide (CO) gas has been extensively applied in the bulk chemical industry, its intrinsic Received 10 November 2016 properties such as high toxicity, flammability, and special equipment requirement for handling, limit its Accepted 16 January 2017 utilization in organic synthesis, fine chemical industry and academia. Recently, considerable effort has Available online 18 January 2017 been devoted to the development of CO surrogates to avoid the direct use of carbon monoxide gas. Among the various CO surrogates, formic acid and formaldehyde, have a broad range of applications in Keywords: organic synthesis. The direct carbonylation with formic acid (HCOOH) and formaldehyde (HCHO) repre- Carbonylation sents one of the most atom-economical substitutes owing to their high weight percentage of CO. In this Transition-metal catalysis review, the potential roles of both formic acid and formaldehyde in transition-metal catalyzed carbony- Non-gaseous C1 source CO surrogates lation reactions are discussed. In order to understand these transfer carbonylation reactions, the mecha- nistic rationale for representative examples is also provided. Ó 2017 Elsevier B.V. All rights reserved. Contents 1. Introduction . ....................................................................................................... 44 2. Formic acid as CO surrogates . .................................................................................... 44 2.1. Palladium-catalyzed carbonylation of aryl halides with HCOOH . ....................................................... 45 2.2. Palladium-catalyzed hydroxycarbonylation of arenes with HCOOH . ....................................................... 46 2.3. Palladium or ruthenium-catalyzed carbonylation of alkenes with HCOOH. .................................... 47 2.4. Palladium or nickel-catalyzed hydrocarboxylation of alkynes with HCOOH . .................................... 48 3. Formaldehyde as CO surrogates . .................................................................................... 49 3.1. Rhodium or palladium-catalyzed carbonylation of aryl halides with HCHO . .................................... 49 3.2. Rhodium or ruthenium-catalyzed carbonylation of alkenes with HCHO. .................................... 50 3.3. Rhodium-catalyzed carbonylation of akynes with HCHO . ....................................................... 51 3.4. Rhodium or ruthenium-catalyzed Pauson–Khand-type reaction of 1,6-enynes . .................................... 52 4. Conclusion . ....................................................................................................... 53 Acknowledgements . .................................................................................... 53 References . ....................................................................................................... 53 Abbreviations: Ar, aryl; BINAP, 2,20-bis(diphenylphosphino)-1,10-binaphthyl; BIPHEP, 2,20-bis(diphenylphosphino)-1,10-biphenyl; BMIMCl, 1-butyl-3-methylimidazolium chloride; C1, one carbon; CO, carbon monoxide; COD, cycloocta-1,5-diene; CO2, carbon dioxide; Cy, cyclohexyl; DMF, dimethylformamide; DMSO, dimethyl sulfoxide; dtbpx, a,a0-bis(di-tert-butylphosphino)-o-xylene); DPEphos, bis[2-(diphenylphosphino)phenyl]ether; dppf, 1,10-bis(diphenylphosphino)ferrocene; dppb, 1,4-bis(diphenylpho sphino)butane; dppbz, 1,2-bis(diphenylphosphino)-benzene; dppen, cis-1,2-bis(diphenylphosphino)ethylene; dppp, 1,3-bis(diphenylphosphino)propane; dpppy, diphenyl- 2-pyridylphosphine; HCOOH, formic acid; HCHO, formaldehyde; Nixantphos, 4,6-bis(diphenyl phosphino)phenoxazine; NMP, N-methyl-2-pyrrolidone; Ph-BPE, 1,2-bis-(2,5- diphenylphospholano)ethane; Piv, pivalate; PTSA, p-toluenesulfonic acid; SDS, sodium dodecylsulfate; TPPTS, triphenylphosphane-3,30,300-trisulfonic acid trisodium salt; XantPhos, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene. ⇑ Corresponding authors at: Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou 311121, PR China (L.-W. Xu). E-mail addresses: [email protected] (J. Cao), [email protected] (L.-W. Xu). http://dx.doi.org/10.1016/j.ccr.2017.01.005 0010-8545/Ó 2017 Elsevier B.V. All rights reserved. 44 J. Cao et al. / Coordination Chemistry Reviews 336 (2017) 43–53 1. Introduction COCl O O H [Mo(CO)6] Me Si OH N Ph Since the discovery of the Roelen reaction (hydroformylation 11% Ph S O with syngas) in 1938 and the Reppe reaction (hydrocarboxylation (63% CO) O2 12% 12% with carbon monoxide and water) in 1939 [1], transition-metal 13% O O O catalyzed carbonylation reaction using CO has constituted a key O O Cl Cl mainstay of organometallic chemistry, enabling the synthesis of Cl H N H OH H H carbonyl compounds from different alkenes on an industrial scale O [2]. In this reaction, carbon monoxide (CO) gas is most widely used 22% 23% 38% 61% 93% as a C1 source, and the catalytic carbonylation method with tran- sition metal-based catalyst system has been greatly improved in Fig. 2. The weight percentage of CO in typical CO surrogates. the past decades. Despite the extensive utilization of CO or syngas in the bulk chemical industry and academia, it is still more attrac- as COgen (9-methylfluorene-9-carbonyl chloride) and SilaCOgen tive with respect with the use of CO surrogates from the point of (methyldiphenylsilacarboxylic acid) was reviewed by Skrydstrup view of atom economy. In the past decade, numerous carbonyla- and co-workers [8]. All of these work summarized the early devel- tion reactions conducted without the direct use of gaseous CO or opment of CO-free carbonylation catalysis. However, there were syngas were established. Especially in recent years, two tactics few successful examples on the application of formic acid (HCOOH) were developed to address this issue. The first one is to perform or formaldehyde (HCHO) in transition metal-catalyzed carbonyla- carbonylation reaction in one pot with CO generated in situ by tion reaction. CO surrogates. Another strategy is to conduct carbonylation reac- Among CO surrogates and CO precursors, formic acid and tions in a two-chamber reactor in which CO is released from one formaldehyde exhibit obvious advantages (Fig. 1): (1) the process chamber via decomposition of CO precursors and meanwhile will be simple and efficient for carbonylation with CO that could absorbed in the other chamber to undergo desired carbonylation. be generated in-situ under mild conditions without special reac- In 2004, Morimoto and Kakiuchi provided the first review of tors; (2) the transformation will be more atom-economic for carbonylation reactions with CO surrogates [3]. Since then, much formaldehyde and formic acid possessing high weight percentage more efforts have been invested in search new CO surrogates for of CO (ca. 93 wt% and 61 wt% respectively, Fig. 2); (3) the reaction carbonylation reaction from the view point of green organic chem- will be more environment-friendly for hydrogen and water will be istry. In this regard, several reviews focusing on either a specific the only wastes produced in the CO release process. In recent years, surrogate or a class of substrate have also been published. For considerable progress has been achieved in this area. However, example, Odell and co-workers summarized recent progress in there is no thorough summary on the carbonylation reactions with the carbonylation using molybdenum hexacarbonyl as a solid sur- formaldehyde and formic acid as the CO surrogates. In this review, rogate [4]. Beller et al. reported carbonylation of alkenes using CO we focused our attention on the development of new catalytic sys- surrogates [5]. Konishi and Manabe published a topic focusing on tem for the carbonylation of simple alkenes, alkynes, or organic formic acid derivatives such as phenyl formate and N- halides using HCHO or HCOOH as non-gaseous carbonyl C1 formylsaccharin as CO surrogates [6]. Bhanage and co-workers sources. We will provide comprehensive coverage of ‘‘CO-free” car- summarized transition-metal catalyzed carbonylation of alkynes, bonylation reactions that can be conducted with cheap and readily arenes and aryl halides using CO surrogates [7]. On the other hand, available HCHO or HCOOH according to the category of substrates. the two-chamber reactor strategy employing CO precursors such O O 2. Formic acid as CO surrogates C C O R' NHR'' R' O O C R'COOH C C R'' R' OR'' It is well-known that formic acid readily decomposes to carbon R' OR'' O monoxide and water under acidic conditions and at elevated tem- O [O] peratures. With appropriate activators, formic acid could be uti- C CO CO2 R' O O R'' R' R'' [H] lized in transition-metal catalyzed carbonylative reactions, in which CO would be released in-situ under mild conditions. Early [M] [M] research revealed that formic acid could
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