Carbonyl allylboration reaction

Ever since the discovery that allylboranes could add in a nucleophilic fashion to aldehydes and ketones in 1964,carbonyl allylboration reactions have been thoroughly utilized in organic chemistry. Modification of allylic boron reagents and the substrates with which they can react has been the focus of many research groups over the past three decades. The application of allylbor-onates in the context of aldehyde allylation, which results in the formation of homoaUylic secondary alcohols via an allyl transfer reaction with aldehydes, has become an invaluable tool to synthetic chemists (Figure 3). ... 

The presence of a stereogenic center on the aldehyde can strongly inlinence the diastereoselectivity in allylboration reactions, especially if this center is in the a-position. Predictive rules for nucleophilic addition on snch a-snbstitnted carbonyl substrates such as the Felkin model are not always snitable for closed transition structures.For a-substituted aldehydes devoid of a polar substituent, Roush has established that the minimization of ganche-ganche ( syn-pentane ) interactions can overrule the influence of stereoelectronic effects. This model is valid for any 3-monosubstituted allylic boron reagent. For example, althongh crotylboronate (E)-7 adds to aldehyde 39 to afford as the major prodnct the diastereomer predicted by the Felkin model (Scheme 2), " it is proposed that the dominant factor is rather the minimization of syn-pentane interactions between the Y-snbstitnents of the allyl unit and the a-carbon of the aldehyde. With this... 

Although Brown and co-workers proposed a six-membered transition state for the asymmetric allylboration reaction in which the aldedyde oxygen initially coordinates to boron followed by an internal transfer of the allyl group from boron to the carbonyl carbon,8 a quantitative analysis to explain the enantioselectivity was not available until 1993, when Gennari et al. conducted a computational study to rationalize the enantiofacial selectivity of Brown allylation9 (Scheme 3.1g). Calculation predicts that transition state A, in which the allyl group attacks the si-lace of the aldehyde, is favored over transition state B by 2.12kcal/mol. 

Generally the reaction of unsaturated aldehydes (aromatic, olefmic and acetylenic) with chiral boronates has provided homoallylic alcohols in low to moderate enantioselectivity [124]. However, the enantioselectivity of the allyl- and 2-bu-tenylborations of benzaldehyde and unsaturated aldehydes is significantly improved when a metal carbonyl complex is utilized as the substrate [131]. For example, the reaction of iron carbonyl-complexed diene 225, chromium carbonyl-complexed benzaldehyde 226 and dicobalt hexacarbonyl-complexed acetylene 227 all give significantly increa.sed allyl and 2-butenylboration selectivities compared to the parent aldehydes (Fig. 10-6). In the case of chiral substrates 225 and 226, these species can be obtained in enantioenriched form by kinetic resolution by use of the asymmetric allylboration reaction. 

The reaction tolerated various functional groups, thus allowing the in situ preparation of allylboron compounds possessing a carbonyl group (Equation (32)).236 The tandem diboration-intramolecular allylboration provided a diastereoselective access to the cycloalkanes bearing 1,3-diols. 

Selected allyl boronates synthesized according to Equation (57) are shown in Scheme 18. The reaction provided a convenient access to allylboranes possessing a carbonyl group 168 and 169,310,311 which underwent in situ intramolecular allylboration. A variety of 5-5, 6-5, and 7-5 m-fused exomethylene cyclopentanols were synthesized... 

The following reactions proceed with the participation of the allylic boron system (i) allylboration and protolytic cleavage of organic compounds with multiple bonds, (ii) allylboron-alkyne condensation,598 599 (iii) reductive mono-and trans-a,a -diallylation of nitrogen aromatic compounds, (iv) disproportionation processes between tribut-2-enylborane and BX3 (X = C1, Br, OR, SR). Allylboration of carbonyl compounds, thioketones, imines, or nitriles leads to the homoallylic alcohols, thiols, or amines (Equations (136) and (137). It is most important that 1,2-addition to aldehydes and imines proceeds with high diastereoselectivity so that ( )-allylic boranes and boronates give the anti-products, while -products are formed preferentially from (Z)-isomers. 

The reaction of 54e with acetone proceeds smoothly at -10°C to give borinic ester 55 (Scheme 2.33) [50]. Since the allylboration of carbonyl... 

The stability of allylboronates and the high level of diastereoselectivity in their additions to carbonyl compounds and imines represent very attractive attributes in organic synthesis. The examples in this chapter clearly show that recent advances in the preparation of allylboronates will help in furthering their applications. The development of efficient catalytic enantioselective allylboration methods and the invention of more powerful and more elaborate tandem reaction processes constitute two emerging areas for further development. 

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