Borinates

The reaction undergone by alcohols with trialkyl- and triaryl-boranes in the presence of pivalic acid, to give borinic esters, and the thermal cyclization of bis(dialkylborinates) to boronates, are discussed briefly in Section II. Many borinates have been prepared in quantitative yield from mono-, di-, oligo-, and poly-saccharides,338,108 and mixed 

At pH 10, diphenylborinic acid gives a tetrahedral anion that complexes with various diol systems, and thus it can be used in electrophoresis like borate.109 In a more detailed study of such complexing,110 diols were examined by 13C-n.m.r. spectroscopy, before and after addition of sodium diphenylborinate, and complexes were detected, and their spectra observed, for a variety of carbohydrate derivatives. 1,2-Diol groupings in acyclic and cis-cyclic compounds, 1,3-related diols at C-4,C-6 of hexopyranosides, the 3,5-diols of glucofuranoses, and 2,4-diols of the anomeric methyl 3,6-anhydro-D-glucopyranosides were all found to react. No interaction occurred with l,6-anhydro-/3-D-glucopyranose (compare Section V,2). 

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When immediately followed by -in or -ine, phospha- should be replaced by phosphor-, arsa- by arsen-, and stiba-by antimon-. The saturated six-membered rings corresponding to phosphorin and arsenin are named phosphorinane and arsenane. A further exception is the replacement of borin by borinane. 

Boraanthracene — see Dibenzo[6,e]borin 9-Boraanthracene anions nomenclature, 1, 631 Borabenzene anions nomenclature, 1, 631... 

Dibenzo[6,e]borinate, 5-aryl, 1, 642 Dibenzo[b,e]borinate, 5-mesityl-synthesis, 1, 643 Dibenzo[b,e]borinate, 5-phenyl-lithium salt... 

By employing optically active enol borinates instead of silylketene acetals, the Ireland-Claisen rearrangement has been further developed to an enantioselective... 

Isopinocampheyl(l-isopinocampheyl-2-octenyl)borinic acid (1), available with a diastereomer-ic purity of approximately 80 85% de, reacts smoothly with aldehydes at —15 °C in tetrahy-drofuran to provide a homoallylic alcohol with 79-85% ee after oxidative workup (30% hydrogen peroxide, 40 °C)6. 

Improved methods for the preparation of reagents such as isopinocampheyl(l-isopinocam-pheyl-2-alkenyl)borinic acids will certainly lead to a more enantioselective synthesis of anti-homoallylic alcohols, since the enantiomeric purity of the reagent is the only significant limitation to the synthetic utility of this reagent system. 

The enantiomeric /1-hydroxy ketones are available in an analogous way using the corresponding enantiomeric borinates. The reaction is plagued by low regioselectivity in the formation of the boron enolates, except when R1 is phenyl or isobutyl53,57. 

Methyl Borate (Trimethyl borate or Trimethoxy borine), (CH3.0)3B, mw 103.92, OB to C02 — 115.47, colorl liq, mp —29°, bp68°,d 0.92 g/cc at 20° vap d 3.59. Prepn other properties are given in Beil (Ref l). Sax (Ref 2) lists this compd as a dangerous fire hazard when exposed to heat or flame. It reacts with w or steam to produce toxic flammable vapors, and vigorously with oxid materials Refs 1) Beil 1, 287, (143) [275] 2) Sax... 

The enol acetates, in turn, can be prepared by treatment of the parent ketone with an appropriate reagent. Such treatment generally gives a mixture of the two enol acetates in which one or the other predominates, depending on the reagent. The mixtures are easily separable. An alternate procedure involves conversion of a silyl enol ether (see 12-22) or a dialkylboron enol ether (an enol borinate, see p. 560) to the corresponding enolate ion. If the less hindered enolate ion is desired (e.g., 126), it can be prepared directly from the ketone by treatment with lithium diisopropylamide in THE or 1,2-dimethoxyethane at —78°C. ... 

Regioselectivity in the halogenation of unsymmetrical ketones can be attained by treatment of the appropriate enol borinate of the ketone with NBS or NCS. The desired halo ketone is formed in high yield. Another method for achieving the... 

Among the preformed enol derivatives used in this way have been enolates of magnesium, lithium, titanium, zirconium, and tin, ° silyl enol ethers, enol borinates,and enol borates, R CH=CR"—OB(OR)2. The nucleophilicity of silyl enol ethers has been examined. In general, metallic Z enolates give the syn (or erythro) pair, and this reaction is highly useful for the diastereoselective synthesis of these products. The ( ) isomers generally react nonstereoselectively. However, anti (or threo) stereoselectivity has been achieved in a number of cases, with titanium enolates, with magnesium enolates, with certain enol bor-inates, and with lithium enolates at — 78°C. ... 

For conversion of ketones to either (Z) or ( ) enol borinates, see, for example, Evans,... 

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