With organoboranes

P-chlorocarbamates which can be converted to aziridines and alkyloxazoUdones (93,115). A/-Chloro-A/-sodiourethane reacts with organoboranes forming A/-alkylcarbamates (114), and with olefins, catalyzed by Os, forming vicinal hydroxy carbamates (116). 

ArSnRs, and with arylmercury compounds. Aryl triflates react with arylbo-ronic acids ArB(OH)2, or with organoboranes, in the presence of a palladium catalyst, to give the arene in what is called Suzuki couplingCyclopropyl groups can be attached to aromatic rings by this reaction. Even hindered boronic acids give good yields of the coupled product. 

B. M. Trost, ed., Stereodirected Synthesis with Organoboranes, Springer, Berlin, 1995. 

The significance of B—C ir-bonding in determining the course and the ease of chemical reaction with organoboranes is obviously a more difficult question for both the experimentalist and the theoretician. Again, both inductive and resonance effects can, in principle, play a role but in addition, steric effects now become important, either for intramolecular reactions, as in Eq. (5), or for intermolecular reactions, as in Eqs. (7, 8). 

Alkylzirconocene derivatives can be converted to alcohols with H202/NaOH, /BuOOH, or m-chloroperbenzoic acid (m-CPBA) [98], These reactions appear to involve migratory insertion processes (Pattern 14) similar to those observed with organoboranes (Scheme 1.20). On the other hand, oxidation with 02 may be a radical process. 

A-Lithium and A-potassium derivatives of A-Boc 0-p-tosylhydroxylamines have been also reported to react rapidly with organoboranes to give A-Boc protected primary amines in modest to good yields (Scheme 28) . 

C. Chen, K. Wilcoxen, C.Q. Fluang, N. Strack, J.R. McCarthy, New methods for the synthesis of fluoro olefins via the palladium catalyzed cross-coupling reaction of 1-fluorovinyl halides with organoboranes and organostannanes, J. Fluor. Chem. 101 (2000) 285-290. 

Reductive carbonylation and alkylation of imines.3 This cobalt carbonyl catalyzes a reaction of imines with organoboranes and carbon monoxide that results in amides. / -Keto amides are obtained from a-keto imines by this reaction. 

It was also reported that terminally borane-containing POs is available as another macroinitiator to prepare block copolymers (Fig. 4). These polymers were prepared by (1) the metallocene-catalyzed (co)polymerization of olefin(s) with organoborane compounds, for example, 9-borabicyclononane (9-BBN), as chain transfer agents [32], or by (2) the hydroboration of terminally unsaturated polyolefins with BBN [33-36]. 

M. M. Midland, Asymmetric Reduction with Organoborane Reagents, Chem. Rev. 1989, 89, 1553. 

The reaction of trialkylboranes with iV-chloroalkylamines can be used to synthesize a wide variety of functionally substituted dialkylamines in good yields [66,67], and it complements the synthesis of secondary amines via the reaction of trialkylboranes with organic azides. The reaction is analogous to the reaction of chloramine with organoboranes, and presumably occurs via an anionotropic migration of an alkyl group from boron to nitrogen (Scheme 24). 

The reaction of dialkylchloramines with organoboranes gives tertiary amines, if the competitive free radical reaction leading to the formation of alkylchlorides is suppressed by adding of a radical scavenger such as galvinoxyl [72,73] (Scheme 26). 

E. Block, Olefin synthesis via deoxygenation of vicinal diols, Org. React. (N.Y.) 1984, 30, 457. M. M. Midland, Asymmetric reduction with organoborane reagents, Chem. Rev. 1989,89, 1553. H. C. Brown and P. V. Ramachandran, Asymmetric reduction with chiral organoboranes based... 

The light induced reactions of bromine with organoboranes proceed through a-bro-mination 38) followed by facile migration of an alkylgroup in the presence of nucleophiles, such as water 39,40) (Eq. 1). Thus, this sequence provides means of coupling... 

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