Stereoselective dioxirane hydroxylations and the synthesis of tripod boronic acid esters

Abstract Methyl(trifluoromethyl)dioxirane (TFDO, 1b), a powerful yet selective oxidant, was employed to achieve in high yield the direct stereoselective hydroxylation at tert-CH of cis,cis-1,3,5-trimethylcyclohexane (4), yielding triol 7 bearing all-axial disposition of the three OH groups. Similarly, TFDO oxidation of 1,3- and of 1,4-dimethylcyclohexane gave the corresponding Z-diols 5 and 6, respectively. Triol 7 was a convenient starting material to synthesize a novel borate—that is, 1-bora-2,8,9-trioxa-3,5,7-trimethyladamantane (8)—having a peculiar cage-shaped ‘tripod’ structure. From triol 7, novel tripod arylboronic Bronsted-assisted Lewis acids (BLA) could be obtained, as exemplified by 10a and 10b.

[1]  D. Grant,et al.  Carbon-13 magnetic resonance. IX. Methylcyclohexanes , 1967 .

[2]  Norio Miyaura,et al.  Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds , 1995 .

[3]  O. Sciacovelli,et al.  On the isolation and characterization of methyl (trifluoromethyl) dioxirane , 1988 .

[4]  S. Yamasaki,et al.  Cage-shaped borate esters with enhanced Lewis acidity and catalytic activity. , 2006, Organic letters.

[5]  D. Nakashima,et al.  Reversal of Chemoselectivity in Diels−Alder Reaction with α,β-Unsaturated Aldehydes and Ketones Catalyzed by Brønsted Acid or Lewis Acid , 2005 .

[6]  Wei Wang,et al.  Boronic Acid-Based Sensors , 2002 .

[7]  Keith Smith,et al.  Preparation of trans,trans,trans- and cis,cis,trans-perhydrophenalen-9-ols by application of the three-migration cyanoborate process to isomeric perhydro-9b-boraphenalenes: differences between the cyanoborate and carbonylation reactions , 1978 .

[8]  Steven A Benner,et al.  2-Hydroxymethylboronate as a reagent to detect carbohydrates: application to the analysis of the formose reaction. , 2006, The Journal of organic chemistry.

[9]  B. Marples,et al.  Dioxirane mediated steroidal alkene epoxidations and oxygen insertion into carbon-hydrogen bonds , 1991 .

[10]  M. Smietana,et al.  Selective fluorescence-based detection of dihydrouridine with boronic acids , 2006 .

[11]  B. Wang,et al.  Substituent effect on anthracene-based bisboronic acid glucose sensors , 2006 .

[12]  K. Ishihara,et al.  A New Powerful and Practical BLA Catalyst for Highly Enantioselective Diels−Alder Reaction: An Extreme Acceleration of Reaction Rate by Brønsted Acid , 1996 .

[13]  Akira Suzuki,et al.  Recent advances in the cross-coupling reactions of organoboron derivatives with organic electrophiles, 1995–1998 , 1999 .

[14]  L. D’Accolti,et al.  A novel approach to the efficient oxygenation of hydrocarbons under mild conditions. Superior oxo transfer selectivity using dioxiranes. , 2006, Accounts of chemical research.

[15]  A. Segre,et al.  “Anomalous” Chemical Shifts in the Nuclear Magnetic Resonance Spectra of the 1,3,5-Trimethylcyclohexanes , 1967 .

[16]  A. Basu,et al.  3-Methoxycarbonyl-5-nitrophenyl boronic acid: high affinity diol recognition at neutral pH. , 2004, Bioorganic & medicinal chemistry letters.

[17]  Sambasivarao Kotha,et al.  Recent applications of the Suzuki–Miyaura cross-coupling reaction in organic synthesis , 2002 .

[18]  R. H. Eastman,et al.  Replacement of Hydrogen at a Tertiary Carbon Atom with OH by Alkaline Permanganate1 , 1960 .

[19]  Y. Chien,et al.  Efficient and convenient nonaqueous workup procedure for the preparation of arylboronic esters. , 2002, The Journal of organic chemistry.

[20]  C. Fusco,et al.  Oxidations by methyl(trifluoromethyl)dioxirane. II: Oxyfunctionalization of saturated hydrocarbons , 1989 .

[21]  R. Murray,et al.  Synthesis of Epoxides Using Dimethyldioxirane: trans‐Stilbene Oxide , 2003 .

[22]  D. Matteson.  Boronic Esters in Stereodirected Synthesis , 1989 .