Boronic acid derivatives reactions

The transition metal catalyzed cross coupling of an organohalide with a boronic acid derivative, the Suzuki-Miyaura coupling, has become one of the most popular ways of preparing biaryls.3 The reaction is very robust and can easily be scaled to provide multigrams of material.4... 

FuNn iONAL Group Tolerance of PdildbrO VIMes.HCI Catalyzed Suzuki Cross-Coupling Reactions of Aryl Chlorides with Phenyi.boronic Acid Derivatives... 

Typically, the boronic acid group is part of an aminophenyl boronic acid derivative, and this group has been used for bioconjugation and affinity chromatography purposes (Burnett et al., 1980 O Shannessy and Quarles, 1987). A common partner for a phenyl boronic acid group in bioconjugation is the salicylhydroxamic acid (SHA) group (Chapter 17, Section 3) (Reaction 59). 

Carbohydrate detection is important for applications such as glucose monitors these are arguably one of the most successful and relevant biosensors. An interesting fluorescence recovery-type saccharide sensor based on the reactivity of carbohydrates with boronic acids was reported in 2002 [36]. Specifically, modification of the cationic viologen-linked boronic acid derivative 40 to a zwitterionic species 41 upon covalent and reversible reaction of boronic acid with monosaccharides (Scheme 1) can cause the dissociation of the ion-pair in-... 

The reaction is initiated by addition of the amine 2 to the a keto acid 3, catalyzed by the vinyl boronic acid derivative 1. Use orbital interaction theoretical arguments to explain the following features of this synthesis ... 

Reaction between 2-aminobenzamides and boronic acid derivatives give 1,2-dihydro-... 

The one-step reaction among an amine, a carbonyl and a boronic acid derivative is a highly versatile multicomponent reaction that utilizes readily available compo-... 

Arylmethyl(homobenzyl)ethylsulfonium salts are appropriate substrates for Suzuki-type coupling reactions. In this reaction, performed on a polymer-bound sulfonium tetrafluoroborate, the benzyl fragment on the sulfur atom was transferred to the boronic acid residue. The sulfonium salt was prepared from an al-kylthiol resin by alkylation with a substituted benzyl halide to give thioether 98 and subsequent alkylation with triethyloxonium tetrafluoroborate. Reaction with a boronic acid derivative yielded diaryl methanes 99 [94] (Scheme 6.1.22). 

A new synthetic approach to polycyclic aromatic compounds has been developed based on double Suzuki coupling of polycyclic aromatic hydrocarbon bis(boronic acid) derivatives with o-bromoaryl aldehydes to furnish aryl dialdehydes. These are then converted to larger polycyclic aromatic ring systems by either (a) conversion to diolefins by Wittig reaction followed by photocyclization, or (b) reductive cyclization with trifluoromethanesulfonic acid and 1,3-propanediol (Eq. (12)) [30]. 

Because of the different reactivities of iodo and bromo substituents in the Suzuki reaction, selective coupling can be realized. For example, 8-bromo-2-(4-methoxyphenyl)-l,10-phenanthroline (15) can be prepared by reacting the 4-boronic acid derivative of anisole with bromo(iodo)phenanthroline under Suzuki conditions (Eq. (44)) [75]. 

The scope and limitations of Pd(0)-mediated coupling reactions between aromatic halides linked to a polystyrene resin and boronic acid derivatives (Suzuki coupling) or arylstannanes (Stille coupling) have been reported. For all the reactions, the conditions were optimized and evaluated with various reagents. In most cases, products were obtained in excellent yields upon cleavage from the solid support (Eq. (63)) [101]. 

Conceptually this new three-component reaction resembles the methods applied by Steglich, Enders et al. [8a] and Yamamoto et al. [8b], who treated the preformed iminoesters 26 and 29 at low temperature with the electron-rich olefins 27 and 30, respectively [9]. However, the use of boronic acid derivatives appears to be a versatile method with a great deal of potential. As Petasis and Zavialov note at the end of their paper, unprotected amino acids and peptides, aryl boronic acids, and chiral boronates can also participate in their three component condensation [7a]. Transition metal catalysis also... 

Facile synthesis of simple 3-arylpyrroles from pyrroline by tandem Suzuki dehydrogenation reaction is depicted in Scheme 229. Thus, treatment of l-benzyl-2,5-dihydro-l//-pyrrol-3-yl trifluoromethanesulfonate 1195 (prepared in 55% yield from l-benzyl-3-pyrrolidinone 1194 by trapping the enolate with a triflating reagent), with boronic acid derivatives leads to the formation of 3-arylpyrroles 1196 in good yields (65-74%) <2000TL3423>. 

R.A. Batey and co-workers developed a modification of the Petasis-boronic acid-Mannich reaction that occurs via N-acyliminium ions derived from A/-protected-2,3-dihydroxypyrrolidine and 2,3-dihydroxypiperidine derivatives. This method was utilized in the total synthesis of (+)-deoxycastanospermine. The formation of the A/-acyliminium ion was achieved by treating A/-Cbz-2,3-pyrrolidine with BF3-OEt2. ° Subsequent vinyl transfer from the alkenylboronic ester provided the product with excellent yield and diastereoselectivity. 

The procedures described in Chapters 4-7 all relate to a set of broadly similar transformations that are becoming exceptionally important and well used in laboratories worldwide. In Chapter 4, eight examples of the Suzuki coupling reaction are described four accounts describe the use on activated alkene (vinyl bromide, triflate or tosylate) as the coupling partner for boronic acid derivatives. The other examples of Suzuki couplings involve aryl bromides and aryl chlorides. It is noteworthy that the methodology introduced by Nolan has been extended to include amination reactions. 

The most common methods of X—B—X ring construction employ condensation reactions of boronic acid derivatives with y-diamines, diols, and amino alcohols. Specific examples of these processes are presented in the following sections 6.28.4.1-6.28.4.6. 

Boronic acid derivatives undergo condensation reactions with o-aminobenzamide to produce... 

Halogenation of vinylboranes generates vinyl halides. Both cis and trans halides are available by modification of the reaction conditions. When trans-alkenyl boronic acid (73, derived from 1-octyne) was treated with iodine and sodium hydroxide, trans-1-iodo-l-octene (74) was formed in 90%. When the boronic acid was treated with iodine and then with base, the (Z)-alkenyl iodide (75) was produced.Vinylboranes derived from internal alkynes lead to cis-trans mixtures with both of these procedures. Boronic acids derived from alkynes and catecholborane give the (Z)-bromide on addition of bromine followed by sodium hydroxide. ... 

Boronic acids derived from 3- and 5-substituted indoles are useful intermediates for palladium-catalyzed vinylation, arylation, and heteroarylation (Equation (47)) <92H(34)1395, 93TL2235>. As with the stannanes, a reverse process can be utilized. 6- and 7-Bromoindole can be coupled directly with arylboronic acids to give the 6- and 7-arylindoles, respectively a feature of the reaction is that protection of the indole nitrogen is unnecessary (Equation (48)) <94SL93>. A new route to 2-substituted indoles has been developed from trialkyl-(l-methylindol-2-yl)borates. The borate (153),... 

HC(44/3)l>. The two most important methods are (i) conversion of thienyllithium to a thienyl-boronic acid by reaction with alkyl borate, followed by oxidation with H2O2, and (ii) reaction of thienylmagnesium derivatives with t-butylperbenzoate, followed by dealkylation of the /-butyl ethers with acid. The boronic acid method has been used for the synthesis of several pyridine-substituted hydroxy thiophenes <92ACS654>. 

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