MIDLAND Asymmetric Reduction

M. M. Midland, Asymmetric Reductions with Chganoborane Reagents, Chem. Rev. 1989, 89,1553-1561. 

E. Block, Olefin synthesis via deoxygenation of vicinal diols, Org. React. (N.Y.) 1984, 30, 457. M. M. Midland, Asymmetric reduction with organoborane reagents, Chem. Rev. 1989,89, 1553. H. C. Brown and P. V. Ramachandran, Asymmetric reduction with chiral organoboranes based... 

M. Mark Midland and Richard S. Graham 57 ASYMMETRIC REDUCTION OF a,8-ACETYLENIC KETONES WITH B-3-PINANYL-9-BORABICYCLO-[3.3.1DN0NANE (R)-(+)-1-0CTYN-3-0L... 

Midland and others reported that B-isopinocampheyl-9-borabicyclo[3.3.l]no-nane [Alpine-Borane (7 )-79] is an effective reagent for the highly asymmetric reduction of alkynyl ketones to afford the propargylic alcohol 8030 (Scheme 4.3z). The reagent (R)-19 is prepared from (+)-a-pinene and 9-borabicyclo[3.3.1]no-nane (9-BBN) and often represented as 19banana. The levels of asymmetric... 

Midland and Graham completed a total synthesis of (-)-pestalotin (81)33 (Scheme 4.3bb). The asymmetric reduction of the ketone 82 gave the propar-gylic alcohol 83 with high enantioselectivity. Partial reduction of the alkyne,... 

Related reactions Luche reduction, Midland alpine borane reduction, Noyori asymmetric reduction ... 

Midland, M. M., Tramontane, A., Kazubski, A., Graham, R. S., Tsai, D. J. S., Cardin, D. B. Asymmetric reductions of propargyl ketones. An effective approach to the synthesis of optically active compounds. Tetrahedron 1984,40, 1371-1380. 

Midland, M. M., Lee, P. E. Efficient asymmetric reduction of acyl cyanides with B-3-pinanyl 9-BBN (Alpine-borane). J. Org. Chem. 1985, 50, 3237-3239. 

Midland, M. M McLoughlin, J. I., Gabriel, J. Asymmetric reductions of prochiral ketones with B-3-pinanyl-9-borabicyclo[3.3.1]nonane (Alpine-Borane) at elevated pressures. J. Org. Chem. 1989, 54,159-165. 

Asymmetric Reductions with Organoborane Reagents" Midland. M.M. Chem. Rev., 1989, 89, 1553. 

Midland MM, Tramontane A, Kazubski A, Graham RS, Tsai DJS, Cardinv DB (1984) Asymmetric Reductions of Propargyl Ketones. An Effective Approach to the Synthesis of Optically Active Compounds. Tetrahedron 40 1371... 

Reviews on stoichiometric asymmetric syntheses M. M. Midland, Reductions with Chiral Boron Reagents, in J. D. Morrison, ed., Asymmetric Synthesis, Vol. 2, Chap. 2, Academic Press, New York, 1983 E. R. Grandbois, S. I. Howard, and J. D. Morrison, Reductions with Chiral Modifications of Lithium Aluminum Hydride, in J. D. Morrison, ed.. Asymmetric Synthesis, Vol. 2, Chap. 3, Academic Press, New York, 1983 Y. Inouye, J. Oda, and N. Baba, Reductions with Chiral Dihydropyridine Reagents, in J. D. Morrison, ed., Asymmetric Synthesis, Vol. 2, Chap. 4, Academic Press, New York, 1983 T. Oishi and T. Nakata, Acc. Chem. Res., 17, 338 (1984) G. Solladie, Addition of Chiral Nucleophiles to Aldehydes and Ketones, in J. D. Morrison, ed., Asymmetric Synthesis, Vol. 2, Chap. 6, Academic Press, New York, 1983 D. A. Evans, Stereoselective Alkylation Reactions of Chiral Metal Enolates, in J. D. Morrison, ed., Asymmetric Synthesis, Vol. 3, Chap. 1, Academic Press, New York, 1984. C. H. Heathcock, The Aldol Addition Reaction, in J. D. Morrison, ed., Asymmetric Synthesis, Vol. 3, Chap. 2, Academic Press, New York, 1984 K. A. Lutomski and A. I. Meyers, Asymmetric Synthesis via Chiral Oxazolines, in J. D. Morrison, ed., Asymmetric Synthesis, Vol. 3, Chap. 

Midland MM (1983) Reductions with chiral boron reagents. In Morrison JD (ed) Asymmetric synthesis. Academic, New York, vol 2, chap 2, p 45 Itsuno S (1996) The Alembic, Morton Performance Chemicals 53 1 Fiaud JC, Kagan HB (1969) Bull Soc Chim Fr 2742 Borch RF, Levitan SR (1972) J Org Chem 37 2347 Grundon MF, McCleery DG, WUson JW (1976) Tetrahedron Lett 295 Grundon MF, McCleery DG, WUson JW (1981) J Chem Soc Perkin Trans 1 231 Johnson CR, Stark CJ (1979) Tetrahedron Lett 4713... 

Prior to this work, Mosner and Yamaguchi" reported similar reduction with an LAH-quinine combination however, no example of acetylenic ketone was attempted. In a later study, Midland et al. developed a-pinene-9-Borabicyclo [3.3.1] nonane complex as an excellent reagent for the reduction of a,P-acetylenic ketones and observed high asymmetric induction in aliphatic systems (Table 21.1). 

The synthesis of 112 was then modified to provide a single enantiomer. This called for an asymmetric synthesis of cyclization substrate 111. This was accomplished by Midland reduction of ketone 113 to provide 114 with excellent enantioselectivity (Steroids-21). Alkylation of 114 with the appropriate bromide (prepared from 2-methylfuran according to the procedures described on Steroids-18), followed by a few well-precedented reactions, gave 115, and thence 111 and 112. Application of the Midland reduction is notable. This is a relatively early application of a reagent-controlled asymmetric synthesis. It is also notable that the Midland method works extremely well on alkyl alkynyl ketones (because they look like aldehydes to the reagent) and thus, is well-suited to this application. ... 

Midland, M. M. Greer, S. Tramontano, A. Zderic, S. A. Chiral Trialkylborane Reducing Agents. Preparation of 1-Deuterio Primary Alcohols of High Enantiomeric Purity. J. Am. Chem. Soc. 1979, 101, 2352-2355. Midland, M. M. McDowell, D. C. Hatch, R. L. Tramontano, A. Reduction of a,P-Acetylenic Ketones with B-3-Pinanyl-9-borabicyclo[3.3.1]nonane. High Asymmetric Induction in Aliphatic Systems /. Am. Chem. Soc. 1980,102, 867-9. 

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