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Hydrogen auto-transfer

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(Redirected from Borrowing hydrogen (Hydrogen auto-transfer))
Mechanism of the hydroxyl substitution hydrogen auto-transfer reaction.
Mechanism of one type of carbonyl addition hydrogen auto-transfer reaction involving hydrometalation (step 2).

Hydrogen auto-transfer, also known as borrowing hydrogen, is the activation of a chemical reaction by temporary transfer of two hydrogen atoms from the reactant to a catalyst and return of those hydrogen atoms back to a reaction intermediate to form the final product. Two major classes of borrowing hydrogen reactions exist: (a) those that result in hydroxyl substitution, and (b) those that result in carbonyl addition. In the former case, alcohol dehydrogenation generates a transient carbonyl compound that is subject to condensation followed by the return of hydrogen. In the latter case, alcohol dehydrogenation is followed by reductive generation of a nucleophile, which triggers carbonyl addition. As borrowing hydrogen processes avoid manipulations otherwise required for discrete alcohol oxidation and the use of stoichiometric organometallic reagents, they typically display high levels of atom-economy and, hence, are viewed as examples of Green chemistry.

History

The Guerbet reaction, reported in 1899, is an early example of a hydrogen auto-transfer process. The Guerbet reaction converts primary alcohols to β-alkylated dimers via alcohol dehydrogenation followed by aldol condensation and reduction of the resulting enones. Application of the Guerbet reaction to the development of ethanol-to-butanol processes has garnered interest as a method for the production of renewable fuels. In 1932 using heterogeneous nickel-catalysts Adkins reported the first alcohol aminations that occur through alcohol dehydrogenation-reductive amination. Homogenous catalysts for alcohol amination based on rhodium and ruthenium were developed by Grigg and Watanabe in 1981. The first hydrogen auto-transfer processes that convert primary alcohols to products of carbonyl addition were reported by Michael J. Krische in 2007-2008 using homogenous iridium and ruthenium catalysts.

Hydroxyl substitution

Alcohol aminations are among the most commonly utilized borrowing hydrogen processes. In reactions of this type, alcohol dehydrogenation is followed by reductive amination of the resulting carbonyl compound. This represents an alternative to two-step processes involving conversion of the alcohol to a halide or sulfonate ester followed by nucleophilic substitution

As shown below, alcohol amination has been used on kilogram scale by Pfizer for the synthesis of advanced pharmaceutical intermediates. Additionally, AstraZeneca has used methanol as an alternative to conventional genotoxic methylating agents such as methyl iodide or dimethyl sulfate. Nitroaromatics can also participate as amine precursors in borrowing hydrogen-type alcohol aminations.

The formation of carbon–carbon bonds have been achieved through borrowing hydrogen-type indirect Wittig, aldol, Knoevenagel condensations and also through various carbon nucleophiles. Related to the Guerbet reaction, Donohoe and coworkers have developed enantioselective borrowing hydrogen-type enolate alkylations.

Carbonyl addition

As exemplified by the Krische allylation, dehydrogenation of alcohol reactants can be balanced by reduction of allenes, dienes or allyl acetate to generate allylmetal-carbonyl pairs that combine to give products of carbonyl addition. In this way, lower alcohols are directly transformed to higher alcohols in a manner that significantly decreases waste.

In 2008, borrowing hydrogen reactions of 1,3-enynes with alcohols to form products of carbonyl propargylation was discovered. An enantioselective variant of this method was recently used in the total synthesis of leiodermatolide A.

References

  1. ^ Hamid MH, Slatford PA, Williams JM (2007). "Borrowing Hydrogen in the Activation of Alcohols". Advanced Synthesis & Catalysis. 349 (10): 1555–1575. doi:10.1002/adsc.200600638.
  2. ^ Guillena G, Ramón DJ, Yus M (2007-03-26). "Alcohols as electrophiles in C--C bond-forming reactions: the hydrogen autotransfer process". Angewandte Chemie. 46 (14): 2358–64. doi:10.1002/anie.200603794. PMID 17465397.
  3. ^ Ketcham JM, Shin I, Montgomery TP, Krische MJ (August 2014). "Catalytic enantioselective C-H functionalization of alcohols by redox-triggered carbonyl addition: borrowing hydrogen, returning carbon". Angewandte Chemie. 53 (35): 9142–50. doi:10.1002/anie.201403873. PMC 4150357. PMID 25056771.
  4. ^ Nguyen KD, Park BY, Luong T, Sato H, Garza VJ, Krische MJ (October 2016). "Metal-catalyzed reductive coupling of olefin-derived nucleophiles: Reinventing carbonyl addition". Science. 354 (6310): aah5133. doi:10.1126/science.aah5133. PMC 5130112. PMID 27846504.
  5. Guerbet M (1899). "Action de l'Alcool Amylique de Fermentation sur Son Dérivé Sodé" [Action of Amyl Alcohol Fermentation on Its Soda Derivative]. Comptes rendus de l'Académie des Sciences (in French). 128. Paris: 1002–1004.
  6. Aitchison H, Wingad RL, Wass DF (2016-10-07). "Homogeneous Ethanol to Butanol Catalysis—Guerbet Renewed" (PDF). ACS Catalysis. 6 (10): 7125–7132. doi:10.1021/acscatal.6b01883. S2CID 53363379.
  7. Winans CF, Adkins H (1932-01-01). "The alkylation of amines as catalyzed by nickel". Journal of the American Chemical Society. 54 (1): 306–312. doi:10.1021/ja01340a046. ISSN 0002-7863.
  8. Grigg R, Mitchell TR, Sutthivaiyakit S, Tongpenyai N (1981-01-01). "Transition metal-catalysed N-alkylation of amines by alcohols". Journal of the Chemical Society, Chemical Communications (12): 611–612. doi:10.1039/C39810000611. ISSN 0022-4936.
  9. Watanabe, Yoshihisa; Tsuji, Yasushi; Ohsugi, Yukihiro (1981-01-01). "The ruthenium catalyzed N-alkylation and N-heterocyclization of aniline using alcohols and aldehydes". Tetrahedron Letters. 22 (28): 2667–2670. doi:10.1016/S0040-4039(01)92965-X. ISSN 0040-4039.
  10. Bower JF, Skucas E, Patman RL, Krische MJ (December 2007). "Catalytic C-C coupling via transfer hydrogenation: reverse prenylation, crotylation, and allylation from the alcohol or aldehyde oxidation level". Journal of the American Chemical Society. 129 (49): 15134–5. doi:10.1021/ja077389b. PMID 18020342.
  11. Shibahara F, Bower JF, Krische MJ (May 2008). "Ruthenium-catalyzed C-C bond forming transfer hydrogenation: carbonyl allylation from the alcohol or aldehyde oxidation level employing acyclic 1,3-dienes as surrogates to preformed allyl metal reagents". Journal of the American Chemical Society. 130 (20): 6338–9. doi:10.1021/ja801213x. PMC 2842574. PMID 18444617.
  12. Kim IS, Ngai MY, Krische MJ (May 2008). "Enantioselective iridium-catalyzed carbonyl allylation from the alcohol or aldehyde oxidation level using allyl acetate as an allyl metal surrogate". Journal of the American Chemical Society. 130 (20): 6340–1. doi:10.1021/ja802001b. PMC 2858451. PMID 18444616.
  13. Hamid MH, Slatford PA, Williams JM (2011). "The Catalytic Amination of Alcohols". ChemCatChem. 3 (12): 1853–1864. doi:10.1002/cctc.201100255. ISSN 1867-3899. S2CID 38816793.
  14. Yang Q, Wang Q, Yu Z (April 2015). "Substitution of alcohols by N-nucleophiles via transition metal-catalyzed dehydrogenation". Chemical Society Reviews. 44 (8): 2305–29. doi:10.1039/C4CS00496E. PMID 25661436.
  15. Das, Kuhali; Kumar, Amol; Jana, Akash; Maji, Biplab (2020-03-01). "Synthesis and characterization of N,N-chelate manganese complexes and applications in CN coupling reactions". Inorganica Chimica Acta. 502: 119358. doi:10.1016/j.ica.2019.119358. ISSN 0020-1693. S2CID 214558556.
  16. Berliner MA, Dubant SP, Makowski T, Ng K, Sitter B, Wager C, Zhang Y (2011-09-16). "Use of an Iridium-Catalyzed Redox-Neutral Alcohol-Amine Coupling on Kilogram Scale for the Synthesis of a GlyT1 Inhibitor". Organic Process Research & Development. 15 (5): 1052–1062. doi:10.1021/op200174k. ISSN 1083-6160.
  17. Leonard J, Blacker AJ, Marsden SP, Jones MF, Mulholland KR, Newton R (2015-10-16). "A Survey of the Borrowing Hydrogen Approach to the Synthesis of some Pharmaceutically Relevant Intermediates" (PDF). Organic Process Research & Development. 19 (10): 1400–1410. doi:10.1021/acs.oprd.5b00199. ISSN 1083-6160.
  18. Rubio-Marqués P, Leyva-Pérez A, Corma A (September 2013). "A bifunctional palladium/acid solid catalyst performs the direct synthesis of cyclohexylanilines and dicyclohexylamines from nitrobenzenes". Chemical Communications. 49 (74): 8160–2. doi:10.1039/c3cc44064h. hdl:10251/45848. PMID 23925659.
  19. Black, Phillip J.; Edwards, Michael G.; Williams, Jonathan M. J. (2006). "Borrowing Hydrogen: Indirect "Wittig" Olefination for the Formation of C–C Bonds from Alcohols". European Journal of Organic Chemistry. 2006 (19): 4367–4378. doi:10.1002/ejoc.200600070. ISSN 1099-0690.
  20. Taguchi, Kazuhiko; Nakagawa, Hideto; Hirabayashi, Tomotaka; Sakaguchi, Satoshi; Ishii, Yasutaka (2004-01-01). "An Efficient Direct α-Alkylation of Ketones with Primary Alcohols Catalyzed by [Ir(cod)Cl]2/PPh3/KOH System without Solvent". Journal of the American Chemical Society. 126 (1): 72–73. doi:10.1021/ja037552c. ISSN 0002-7863. PMID 14709065.
  21. Pridmore S, Williams JM (December 2008). "C–C bond formation from alcohols and malonate half esters using borrowing hydrogen methodology". Tetrahedron Letters. 49 (52): 7413–7415. doi:10.1016/j.tetlet.2008.10.059.
  22. Blank, Benoît; Kempe, Rhett (2010-01-27). "Catalytic Alkylation of Methyl-N-Heteroaromatics with Alcohols". Journal of the American Chemical Society. 132 (3): 924–925. doi:10.1021/ja9095413. ISSN 0002-7863. PMID 20047316.
  23. Jana, Akash; Kumar, Amol; Maji, Biplab (2021). "Manganese catalyzed C-alkylation of methyl N -heteroarenes with primary alcohols". Chemical Communications. 57 (24): 3026–3029. doi:10.1039/D1CC00181G. ISSN 1359-7345. PMID 33624678. S2CID 232037523.
  24. Armstrong RJ, Akhtar WM, Young TA, Duarte F, Donohoe TJ (September 2019). "Catalytic Asymmetric Synthesis of Cyclohexanes by Hydrogen Borrowing Annulations". Angewandte Chemie. 58 (36): 12558–12562. doi:10.1002/anie.201907514. PMC 6771629. PMID 31265208.
  25. Doerksen RS, Meyer CC, Krische MJ (October 2019). "Feedstock Reagents in Metal-Catalyzed Carbonyl Reductive Coupling: Minimizing Preactivation for Efficiency in Target-Oriented Synthesis". Angewandte Chemie. 58 (40): 14055–14064. doi:10.1002/anie.201905532. PMC 6764920. PMID 31162793.
  26. Patman RL, Williams VM, Bower JF, Krische MJ (2008). "Carbonyl propargylation from the alcohol or aldehyde oxidation level employing 1,3-enynes as surrogates to preformed allenylmetal reagents: a ruthenium-catalyzed C-C bond-forming transfer hydrogenation". Angewandte Chemie. 47 (28): 5220–3. doi:10.1002/anie.200801359. PMC 2861420. PMID 18528831.
  27. Siu YM, Roane J, Krische MJ (July 2021). "Total Synthesis of Leiodermatolide A via Transfer Hydrogenative Allylation, Crotylation, and Propargylation: Polyketide Construction beyond Discrete Allyl- or Allenylmetal Reagents". Journal of the American Chemical Society. 143 (28): 10590–10595. doi:10.1021/jacs.1c06062. PMC 8529965. PMID 34237219.
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