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Volumn 75, Issue 20, 2010, Pages 7022-7025

Mn(0)-mediated chemoselective reduction of aldehydes. Application to the synthesis of α-deuterioalcohols

Author keywords

[No Author keywords available]

Indexed keywords

CHEMOSELECTIVE REDUCTION;

EID: 77957906330     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo1015618     Document Type: Article
Times cited : (22)

References (51)
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    • (1991) Comprehensive Organic Synthesis , vol.8
  • 5
    • 0001945030 scopus 로고
    • 1st ed., Trost B.M., Fleming I. Eds.; Pergamon Press: Oxford, UK
    • Greeves, N. Comprehensive Organic Synthesis, 1st ed.; Trost, B. M.; Fleming, I., Eds.; Pergamon Press: Oxford, UK, 1991; Vol. 8, pp 1 - 24.
    • (1991) Comprehensive Organic Synthesis , vol.8 , pp. 1-24
    • Greeves, N.1
  • 8
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    • For a recent review of its properties, activation, and synthetic applications see
    • For a recent review of its properties, activation, and synthetic applications see: Concellón, J. M.; Rodríguez-Solla, H.; del Amo, V. Chem.- Eur. J. 2008, 14, 10184-10191
    • (2008) Chem.- Eur. J. , vol.14 , pp. 10184-10191
    • Concellón, J.M.1    Rodríguez-Solla, H.2    Del Amo, V.3
  • 9
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    • 2 (99.9 atom % D, 25 L, -221.50) are considerably more expensive.
    • 2 (99.9 atom % D, 25 L, -221.50) are considerably more expensive.
  • 19
    • 73349100031 scopus 로고    scopus 로고
    • For an overview concerning the importance of chemoselectivity in organic chemistry see
    • For an overview concerning the importance of chemoselectivity in organic chemistry see: Afagh, N. A.; Yudin, A. K. Angew. Chem., Int. Ed. 2010, 459, 262-310
    • (2010) Angew. Chem., Int. Ed. , vol.459 , pp. 262-310
    • Afagh, N.A.1    Yudin, A.K.2
  • 20
    • 77957928069 scopus 로고    scopus 로고
    • Although strictly only 1 equiv of Mn dust is required, we found that 8 equiv gives better, more reliable results (see the S.I.). Interestingly, the excess of Mn dust and Coll.HCl could be reused up to four times with excellent results.
    • Although strictly only 1 equiv of Mn dust is required, we found that 8 equiv gives better, more reliable results (see the S.I.). Interestingly, the excess of Mn dust and Coll.HCl could be reused up to four times with excellent results.
  • 21
    • 77957890662 scopus 로고    scopus 로고
    • Methanol and ethanol can also be used but with lower yields (52% and 34%, respectively).
    • Methanol and ethanol can also be used but with lower yields (52% and 34%, respectively).
  • 22
    • 77957890434 scopus 로고    scopus 로고
    • The reaction was also tried in other common solvents such as acetone, DMF, acetonitrile, benzene, and hexane but the reaction did not take place. The reaction took place in other polar solvents such as MeOH (52%) or EtOH (34%), but with lower yields.
    • The reaction was also tried in other common solvents such as acetone, DMF, acetonitrile, benzene, and hexane but the reaction did not take place. The reaction took place in other polar solvents such as MeOH (52%) or EtOH (34%), but with lower yields.
  • 23
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    • For some selected examples of the synthesis of 1-deuterioalcohols see
    • For some selected examples of the synthesis of 1-deuterioalcohols see: Midland, M. M.; Tramontano, A.; Zderic, S. A. J. Am. Chem. Soc. 1977, 99, 5211-5213
    • (1977) J. Am. Chem. Soc. , vol.99 , pp. 5211-5213
    • Midland, M.M.1    Tramontano, A.2    Zderic, S.A.3
  • 29
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    • 2O.
    • 2O.
  • 39
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    • 8 suggests that THF is also donating hydrogen atoms under the described conditions, although less efficiently than water, taking into account the molar relationship. In fact, control experiments showed that in the absence of water THF is also able to promote the reaction albeit in lower yield and higher reaction times
    • 8 suggests that THF is also donating hydrogen atoms under the described conditions, although less efficiently than water, taking into account the molar relationship. In fact, control experiments showed that in the absence of water THF is also able to promote the reaction albeit in lower yield and higher reaction times
  • 45
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    • In a competitive experiment with a mixture of decanal (1) and benzaldehyde (3) we obtained a 1:2 relationship of the corresponding alcohols 2 and 26. Bearing in mind the reported reduction potentials of benzaldehyde (-0.85 V vs SCE) and aliphatic aldehydes (-1.5 to -1.9 V vs SCE), chemoselectivity cannot be exclusively based on the difference between such reduction potentials
    • In a competitive experiment with a mixture of decanal (1) and benzaldehyde (3) we obtained a 1:2 relationship of the corresponding alcohols 2 and 26. Bearing in mind the reported reduction potentials of benzaldehyde (-0.85 V vs SCE) and aliphatic aldehydes (-1.5 to -1.9 V vs SCE), chemoselectivity cannot be exclusively based on the difference between such reduction potentials: Joyce-Pruden, C.; Pross, J. K.; Li, Y. J. Org. Chem. 1992, 57, 5087-5091
    • (1992) J. Org. Chem. , vol.57 , pp. 5087-5091
    • Joyce-Pruden, C.1    Pross, J.K.2    Li, Y.3
  • 48
    • 0142055513 scopus 로고
    • It is known that metal hydrides are generated on transition metal surfaces from their interaction with water molecules and they could potentially be used in reduction reactions. This possibility remains unexplored, however, probably owing to their fleeting existence. Nevertheless, this posible mechanism cannot be completely ruled out
    • It is known that metal hydrides are generated on transition metal surfaces from their interaction with water molecules and they could potentially be used in reduction reactions. This possibility remains unexplored, however, probably owing to their fleeting existence. Nevertheless, this posible mechanism cannot be completely ruled out: Thiel, P. A.; Madey, T. E. Surf. Sci. Rep. 1987, 7, 211-385
    • (1987) Surf. Sci. Rep. , vol.7 , pp. 211-385
    • Thiel, P.A.1    Madey, T.E.2
  • 49
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    • The possible deuterium atom in the hydroxyl group is removed by aqueous workup of the reaction or by D/H exchange with environmental humidity.
    • The possible deuterium atom in the hydroxyl group is removed by aqueous workup of the reaction or by D/H exchange with environmental humidity.
  • 50
    • 77957911903 scopus 로고    scopus 로고
    • Owing to the acid workup is only required to remove the 2,4,6-collidine obtained during the process, other acid solutions with different pH values or even water can also be used for the workup of this reaction.
    • Owing to the acid workup is only required to remove the 2,4,6-collidine obtained during the process, other acid solutions with different pH values or even water can also be used for the workup of this reaction.
  • 51
    • 77957903357 scopus 로고    scopus 로고
    • All new compounds are fully described in the Supporting Information.
    • All new compounds are fully described in the Supporting Information.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.