B- -9-BBN

Reagents and ConcUtions a) CH2=CHMgBr, CuBr, Me2S, 95% b) 9-BBN, H2O2, then Swem oxidation c) NH2OH, then NaBCNHj, aq. MeOH, pH 3.0,82% d) degassed benzene, reflux, 93% e) Raney Ni, then CH2=N Me2r, THF, 89% () AcCl, MeOH, 56%. 

The other approach to eliminating the concerns about the B-H chain transfer agent is to use trialkylborane (without B-H moiety), e.g., methyl-substituted 9-BBN (Me-B-9-BBN) and trimethylborane (TMB) that have a B-CH3 moiety. Table 8 summarizes Cp2ZrCl2/MAO mediated ethylene polymerization in the presence of the Me-B-9-BBN chain transfer agent. For comparison, triethylborane (TEB) was also used as the chain transfer agent under similar polymerization... 

Table 8 Summary of Cp2ZrCl2/MAO-mediated ethylene polymerization in the presenee of Me-B-9-BBN and TEB chain transfer agents at 50°C...

The iodination reaction can also be conducted with iodine monochloride in the presence of sodium acetate (240) or iodine in the presence of water or methanolic sodium acetate (241). Under these mild conditions functionalized alkenes can be transformed into the corresponding iodides. AppHcation of B-alkyl-9-BBN derivatives in the chlorination and dark bromination reactions allows better utilization of alkyl groups (235,242). An indirect stereoselective procedure for the conversion of alkynes into (H)-1-ha1o-1-alkenes is based on the mercuration reaction of boronic acids followed by in situ bromination or iodination of the intermediate mercuric salts (243). 

The conversion of chiral boronic esters iato optically pure B-aIkyl-9-BBN derivatives followed by reaction with a-bromoketones, a-bromoesters, or a-bromonitriles leads to the homologated P-chiral ketones, esters, and nitriles, respectively (526). 

More recent B-NMR studies at room temperature have shown that (acyloxy)diethylboranes are monomeric also in non-polar solvents like chloroform [(5( B) - 60 ppm] [46]. Under the same conditions the corresponding 9-BBN derivatives are monomeric (both types I and II) or dimeric, depending on the electron-donating or -withdrawing effect of the substituent on the carboxyl group, the temperature, and the concentration of the... 

The 2 1 reaction of 9-BBN with a series of dicarboxylic acids, namely oxalic acid, malonic acid, 2,2-dimethylmalonic acid, and succinic acid, in dimeth-oxyethane gives in some cases dimeric and in other cases macrocyclic (acyloxy)diorganoboranes. This has been proved by IR spectroscopy (all C = O groups are bidentate), B-NMR 5 = 10 ppm) and X-ray crystallography [47]. With oxalic acid two structures are possible (IV and V), of which the first with a five-membered boron heterocycle instead of a four-membered one is the more probable formulation (Fig. 13). 

All examples mentioned so far correspond to reactions between two aromatic groups, however, couplings in which one or both partners are alkyl groups can be achieved using electron-rich boron-based nucleophiles. Fiirstner has reported the use of B-alkyl or 5-allyl methoxy-9-BBN anions for the efficient coupling with some aryl chlorides using an in situ prepared IPr HCl/Pd(OAc)j system [118], Some of the results obtained with these easy-to-handle borate-based nucleophiles are shown below (Scheme 6.34). 

Scheme 10 Total synthesis of petrosins C (98) and D (99) [41] (contd.). Experimental conditions i. (a) 9-BBN, THE, (b) H2O2 ii. MsCl, EtsN, CH2CI2 in. NaBH4, EtOH iv. aqueous HCl V. EDA, THE, Mel vi. K2CO3, MeOH, H2O...

Allylic boranes such as 9-allyl-9-BBN react with aldehydes and ketones to give allylic carbinols. The reaction begins by Lewis acid-base coordination at the carbonyl oxygen, which both increases the electrophilicity of the carbonyl group and weakens the C-B bond to the allyl group. The dipolar adduct then reacts through a cyclic TS. Bond formation takes place at the 7-carbon of the allyl group and the double bond shifts.36 After the reaction is complete, the carbinol product is liberated from the borinate ester by displacement with ethanolamine. Yields for a series of aldehydes and ketones were usually above 90% for 9-allyl-9-BBN. 

Figure 32 The dimeric organoborane chain-transfer agent, 9-BBN dimer (49), used for the in situ incorporation of B-containing group in polyolefins during the termination of a metallocene-catalyzed polymerization. (Adapted from ref. 71.)...

The area of organoboron polymers containing borazine and its derivatives is covered in Chapter 5 of this book by Miele and co-workers. Miele and Bernard also describe the utilization of these polymers in ceramics, fibers, and so on, in Chapter 3 of this book. In this section, the utilization of polymers containing borazine or in some cases the bicyclic boron ligand, 9-BBN, for the production of SiC or Si/C/B fibers is briefly described. Recent advances in polypyrazolylborate or pyrazabole-containing polymers and other boron ring system-derived polymers also have been briefly described. 

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