Mukaiyama hydration explained

The Mukaiyama hydration is an organic reaction involving formal addition of an equivalent of water across an olefin by the action of catalytic bis(acetylacetonato)cobalt(II) complex, phenylsilane and atmospheric oxygen to produce an alcohol with Markovnikov selectivity.[1]

The reaction was developed by Teruaki Mukaiyama at Mitsui Petrochemical Industries, Ltd. Its discovery was based on previous work on the selective hydrations of olefins catalyzed by cobalt complexes with Schiff base ligands[2] and porphyrin ligands.[3] Due to its chemoselectivity (tolerant of other functional groups) and mild reactions conditions (run under air at room temperature), the Mukaiyama hydration has become a valuable tool in chemical synthesis.

Mechanism

In his original publication, Mukaiyama proposed that the reaction proceeded through the intermediacy of a cobalt peroxide adduct. A metal exchange reaction between a hydrosilane and the cobalt peroxide adduct leads to a silyl peroxide, which is converted to the alcohol upon reduction, presumably via action of the cobalt catalyst.

Studies investigating the mechanism of cobalt-catalyzed peroxidation of alkenes by Nojima and coworkers,[4] support the intermediacy of a metal hydride that reacts with the alkene directly to form a transient cobalt-alkyl bond. Homolysis generates a carbon centered radical that reacts directly with oxygen and is subsequently trapped by a cobalt(II) species to form the same cobalt-peroxide adduct as suggested by Mukaiyama. Metal exchange with the hydrosilane produces a silyl peroxide product and further reduction (via homolysis of the oxygen-oxygen bond) leads to the product alcohol. The use of a silane reductant allows for this reaction to be carried out without heat.[5] The authors also note, in accordance with previous studies, that the addition of t-butylhydroperoxide can increase the rate of slower-reacting substrates. This rate increase is likely due to oxidation of cobalt(II) to alkylperoxo-cobalt(III) complex, which subsequently participates in a rapid metal exchange with the hydrosilane to generate the active cobalt(III)-hydride.

The mechanism laid out above is in marked contrast to previous mechanistic proposals,[6] which suggest that a cobalt-peroxy complex inserts directly into alkenes. The aforementioned study by Nojima and coworkers disagrees with this proposal due to three observations: 1) the intermediacy of a cobalt-hydride observed via 1H NMR 2) the propensity of alkenes to undergo autooxidation to the α, β-unsaturated ketones or allylic alcohols when the same reaction is run in the absence of a hydrosilane 3) the predominant mode of decomposition of alkylperoxo-cobalt(III) species to an alkoxy or alkylperoxy radical via the Haber–Weiss mechanism.

A recent review by Shenvi and coworkers,[7] proposed that the Mukaiyama hydration operates via the same principles as metal hydride hydrogen atom transfer (MH HAT), elucidated by Jack Halpern and Jack R. Norton in their studies on hydrogenation of anthracenes by syngas and Co2(CO)8[8] and the chemistry of vitamin B12 mimics,[9] respectively.

Variations

Carbon-oxygen bond formation

Yamada explored the effect of different solvents and cobalt beta-diketonate ligands on the yield and product distribution of the reaction.[10]

Mukaiyama and Isayama developed conditions to isolate the intermediate silylperoxide.[11] [12] Treatment of the intermediate silylperoxide with 1 drop of concentrated HCl in methanol leads to the hydroperoxide product.
Both Mukaiyama[13] and Magnus[14] describe conditions for an α-enone hydroxylation reaction using Mn(dpm)x in the presence of oxygen and phenylsilane. An asymmetric variant was described by Yamada and coworkers.[15]

Dale Boger and coworkers used a variant of the Mukaiyama hydration, utilizing an iron oxalate catalyst (Fe2ox3•6H2O) in the presence of air, for the total synthesis of vinblastine and related analogs.[16]

Carbon-nitrogen bond formation

Erick Carreira’s group has developed both cobalt and manganese-catalyzed methods for the hydrohydrazination of olefins.[17] [18]

Both Carreira[19] and Boger[20] have developed hydroazidation reactions.

Applications

In total synthesis

The Mukaiyama hydration or variants thereof have been featured in the syntheses of (±)-garsubellin A,[21] stigmalone,[22] vinblastine,[23] (±)-cortistatin A,[24] (±)-lahadinine B,[25] ouabagenin,[26] pectenotoxin-2,[27] (±)-indoxamycin B,[28] trichodermatide A,[29] (+)-omphadiol[30] and many more natural products.

In the following diagram, an application of the Mukaiyama hydration in the total synthesis of (±)-garsubellin A is illustrated:

The hydration reaction is catalyzed by Co(acac)2 (acac = 2,4-pentanedionato, better known as acetylacetonato) and carried out in the presence of air oxygen & phenylsilane. With isopropanol used as solvent, yields of 73 % are obtained.

See also

Notes and References

  1. Isayama. Shigeru. Mukaiyama. Teruaki. A New Method for Preparation of Alcohols from Olefins with Molecular Oxygen and Phenylsilane by the Use of Bis(acetylacetonato)cobalt(II). Chemistry Letters. 1 June 1989. 18. 6. 1071–1074. 10.1246/cl.1989.1071. 0366-7022.
  2. Hamilton. Dorothy E.. Drago. Russell S.. Zombeck. Alan. Mechanistic studies on the cobalt(II) Schiff base catalyzed oxidation of olefins by O2. Journal of the American Chemical Society. 1 January 1987. 109. 2. 374–379 . 10.1021/ja00236a014 . 0002-7863.
  3. Okamoto. Tadashi. Oka. Shinzaburo. Oxygenation of olefins under reductive conditions. Cobalt-catalyzed selective conversion of aromatic olefins to benzylic alcohols by molecular oxygen and tetrahydroborate. The Journal of Organic Chemistry. 1 May 1984. 49. 9. 1589–1594. 10.1021/jo00183a020. 0022-3263.
  4. Tokuyasu. Takahiro. Kunikawa. Shigeki. Masuyama. Araki. Nojima. Masatomo. Co(III)−Alkyl Complex- and Co(III)−Alkylperoxo Complex-Catalyzed Triethylsilylperoxidation of Alkenes with Molecular Oxygen and Triethylsilane. Organic Letters. 1 October 2002. 4. 21. 3595–3598. 10.1021/ol0201299. 12375896. 1523-7060.
  5. Zweig. Joshua E.. Kim. Daria E.. Newhouse. Timothy R.. 2017-09-27. Methods Utilizing First-Row Transition Metals in Natural Product Total Synthesis. Chemical Reviews. 117. 18. 11680–11752. 10.1021/acs.chemrev.6b00833. 28525261. 0009-2665.
  6. Hamilton. Dorothy E.. Drago. Russell S.. Zombeck. Alan. Mechanistic studies on the cobalt(II) Schiff base catalyzed oxidation of olefins by O2. Journal of the American Chemical Society. 109. 2. 374–379. 10.1021/ja00236a014. en. 1987.
  7. Crossley. Steven W. M.. Obradors. Carla. Martinez. Ruben M.. Shenvi. Ryan A.. Mn-, Fe-, and Co-Catalyzed Radical Hydrofunctionalizations of Olefins. Chemical Reviews. 10 August 2016. 116. 15. 8912–9000. 10.1021/acs.chemrev.6b00334. 27461578. 5872827.
  8. Halpern. J.. Free radical mechanisms in organometallic and bioorganometallic chemistry. Pure and Applied Chemistry. 1 January 1986. 58. 4. 575–584. 10.1351/pac198658040575. 53710591. en. 0033-4545. free.
  9. Estes. Deven P.. Grills. David C.. Norton. Jack R.. The Reaction of Cobaloximes with Hydrogen: Products and Thermodynamics. Journal of the American Chemical Society. 17 December 2014. 136. 50. 17362–17365. 10.1021/ja508200g. 25427140. 1183829. 0002-7863.
  10. Kato. Koji. Yamada. Tohru. Takai. Toshihiro. Inoki. Satoshi. Isayama. Shigeru. Catalytic Oxidation–Reduction Hydration of Olefin with Molecular Oxygen in the Presence of Bis(1,3-diketonato)cobalt(II) Complexes. Bulletin of the Chemical Society of Japan. January 1990. 63. 1. 179–186. 10.1246/bcsj.63.179. free.
  11. Isayama. Shigeru. Mukaiyama. Teruaki. Novel Method for the Preparation of Triethylsilyl Peroxides from Olefins by the Reaction with Molecular Oxygen and Triethylsilane Catalyzed by Bis(1,3-diketonato)cobalt(II). Chemistry Letters. 1 April 1989. 18. 4. 573–576. 10.1246/cl.1989.573. 0366-7022.
  12. Isayama. Shigeru. An Efficient Method for the Direct Peroxygenation of Various Olefinic Compounds with Molecular Oxygen and Triethylsilane Catalyzed by a Cobalt(II) Complex. Bulletin of the Chemical Society of Japan. 1 May 1990. 63. 5. 1305–1310. 10.1246/bcsj.63.1305. 0009-2673.
  13. Inoki. Satoshi. Kato. Koji. Isayama. Shigeru. Mukaiyama. Teruaki. A New and Facile Method for the Direct Preparation of α-Hydroxycarboxylic Acid Esters from α,β-Unsaturated Carboxylic Acid Esters with Molecular Oxygen and Phenylsilane Catalyzed by Bis(dipivaloylmethanato)manganese(II) Complex. Chemistry Letters. 1 October 1990. 19. 10. 1869–1872. 10.1246/cl.1990.1869. 0366-7022.
  14. Magnus. Philip. Payne. Andrew H. Waring. Michael J. Scott. David A. Lynch. Vince. Conversion of α,β-unsaturated ketones into α-hydroxy ketones using an MnIII catalyst, phenylsilane and dioxygen: acceleration of conjugate hydride reduction by dioxygen. Tetrahedron Letters. 9 December 2000. 41. 50. 9725–9730. 10.1016/S0040-4039(00)01727-5.
  15. Sato. Mitsuo. Gunji. Yasuhiko. Ikeno. Taketo. Yamada. Tohru. Stereoselective Preparation of α-Hydroxycarboxamide by Manganese Complex Catalyzed Hydration of α,β-Unsaturated Carboxamide with Molecular Oxygen and Phenylsilane. Chemistry Letters. 11 September 2004. 33. 10. 1304–1305. 10.1246/cl.2004.1304. 0366-7022.
  16. Ishikawa. Hayato. Colby. David A.. Seto. Shigeki. Va. Porino. Tam. Annie. Kakei. Hiroyuki. Rayl. Thomas J.. Hwang. Inkyu. Boger. Dale L.. Total Synthesis of Vinblastine, Vincristine, Related Natural Products, and Key Structural Analogues. Journal of the American Chemical Society. 8 April 2009. 131. 13. 4904–4916. 10.1021/ja809842b. 19292450. 0002-7863. 2727944.
  17. Waser. Jérôme. González-Gómez. José C.. Nambu. Hisanori. Huber. Pascal. Carreira. Erick M.. Cobalt-Catalyzed Hydrohydrazination of Dienes and Enynes: Access to Allylic and Propargylic Hydrazides. Organic Letters. 1 September 2005. 7. 19. 4249–4252. 10.1021/ol0517473. 16146399. 1523-7060.
  18. Waser. Jérôme. Carreira. Erick M.. Catalytic Hydrohydrazination of a Wide Range of Alkenes with a Simple Mn Complex. Angewandte Chemie International Edition. 6 August 2004. 43. 31. 4099–4102. 10.1002/anie.200460811. 15300706. en. 1521-3773.
  19. Waser. Jérôme. Nambu. Hisanori. Carreira. Erick M.. Cobalt-Catalyzed Hydroazidation of Olefins: Convenient Access to Alkyl Azides. Journal of the American Chemical Society. 1 June 2005. 127. 23. 8294–8295. 10.1021/ja052164r. 15941257. 0002-7863.
  20. Leggans. Erick K.. Barker. Timothy J.. Duncan. Katharine K.. Boger. Dale L.. Iron(III)/NaBH4-Mediated Additions to Unactivated Alkenes: Synthesis of Novel 20′-Vinblastine Analogues. Organic Letters. 16 March 2012. 14. 6. 1428–1431. 10.1021/ol300173v. 22369097. 1523-7060. 3306530.
  21. Kuramochi. Akiyoshi. Usuda. Hiroyuki. Yamatsugu. Kenzo. Kanai. Motomu. Shibasaki. Masakatsu. Total Synthesis of (±)-Garsubellin A. Journal of the American Chemical Society. 1 October 2005. 127. 41. 14200–14201. 10.1021/ja055301t. 16218611. 0002-7863.
  22. Enders. Dieter. Ridder. André. First Asymmetric Synthesis of Stigmolone: The Fruiting Body Inducing Pheromone of the Myxobacterium Stigmatella Aurantiaca. Synthesis. 1 January 2000. 2000. 13. 1848–1851. 10.1055/s-2000-8219. 196825043 . en. 0039-7881.
  23. Ishikawa. Hayato. Colby. David A.. Seto. Shigeki. Va. Porino. Tam. Annie. Kakei. Hiroyuki. Rayl. Thomas J.. Hwang. Inkyu. Boger. Dale L.. Total Synthesis of Vinblastine, Vincristine, Related Natural Products, and Key Structural Analogues. Journal of the American Chemical Society. 8 April 2009. 131. 13. 4904–4916. 10.1021/ja809842b. 19292450. 0002-7863. 2727944.
  24. Shenvi. Ryan A.. Guerrero. Carlos A.. Shi. Jun. Li. Chuang-Chuang. Baran. Phil S.. Synthesis of (+)-Cortistatin A. Journal of the American Chemical Society. 1 June 2008. 130. 23. 7241–7243. 10.1021/ja8023466. 18479104. 2652360. 0002-7863.
  25. Magnus. Philip. Westlund. Neil. Synthesis of (±)-lahadinine B and (±)-11-methoxykopsilongine. Tetrahedron Letters. 2 December 2000. 41. 49. 9369–9372. 10.1016/S0040-4039(00)01399-X.
  26. Renata. Hans. Zhou. Qianghui. Baran. Phil S.. Strategic Redox Relay Enables A Scalable Synthesis of Ouabagenin, A Bioactive Cardenolide. Science. 4 January 2013. 339. 6115. 59–63. 10.1126/science.1230631. 23288535. en. 0036-8075. 2013Sci...339...59R. 4365795.
  27. Bondar. Dmitriy. Liu. Jian. Müller. Thomas. Paquette. Leo A.. Pectenotoxin-2 Synthetic Studies. 2. Construction and Conjoining of ABC and DE Eastern Hemisphere Subtargets. Organic Letters. 1 April 2005. 7. 9. 1813–1816. 10.1021/ol0504291. 15844913. 1523-7060.
  28. Jeker. Oliver F.. Carreira. Erick M.. Total Synthesis and Stereochemical Reassignment of (±)-Indoxamycin B. Angewandte Chemie International Edition. 2 April 2012. 51. 14. 3474–3477. 10.1002/anie.201109175. 22345071. en. 1521-3773.
  29. Shigehisa. Hiroki. Suwa. Yoshihiro. Furiya. Naho. Nakaya. Yuki. Fukushima. Minoru. Ichihashi. Yusuke. Hiroya. Kou. Stereocontrolled Synthesis of Trichodermatide A. Angewandte Chemie International Edition. 25 March 2013. 52. 13. 3646–3649. 10.1002/anie.201210099. 23417860. en. 1521-3773.
  30. Liu. Gang. Romo. Daniel. Total Synthesis of (+)-Omphadiol. Angewandte Chemie International Edition. 8 August 2011. 50. 33. 7537–7540. 10.1002/anie.201102289. 21761524. en. 1521-3773.

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