ALKYLBORANES IN THE SUZUKI-MIYAURA COUPLING - STEREOCHEMICAL AND MECHANISTIC STUDIES

Both erythro and three isomers of B-(3,3-dimethyl-1,2-dideuterio-1-but yl)-9-BBN (6) were prepared from 3,3-dimethyl-1-butyne (4) through a h ydroboration-deuteronolysis-hydroboration sequence employing first 9-B BN-H and then 9-BBN-D, or in reverse order, respectively. Employing th e Whitesides protocol, the stereochemistry of B --> Pd alkyl group tra nsfer in the Suzuki-Miyaura coupling of 6 to PhBr has been found to oc cur with complete retention of configuration with respect to carbon. F or the coupling process, the Lewis acidity of the boron plays an impor tant role with B-alkyl-9-BBN (10) forming [HO(R)-9-BBN](-1) (12) with the added base, in marked contrast to their B-alkyl-9-oxa-10-borabicyc lo[3.3.2]decane counterparts (R-OBBD, 11) which do not. This behavior parallels their coupling rates with the exclusive reaction of 10 over 11 in competitive experiments. Five five possible roles were demonstra ted for the added base in the coupling: (1) the formation of 12, (2) t he hydrolysis of Ph(Ph3P)(2)PdBr (14) to provide monomeric Ph(Ph3P)(2) PdOH (15), (3) the complexation of HOBR2 byproducts which can compete with 10 for base, (4) accelerated coupling rates for 11, and (5) catal yst regeneration. Kinetic studies reveal that the couplings are zero-o rder in the borane but for 10 exhibit a first-order dependence on [PhB r] (i.e., oxidative addition), while for 11 exhibit a first-order depe ndence on [OH-1] (i.e., Pd(II)X hydrolysis). These data are interprete d in terms of attack of 14 by 12 to form a hydroxo mu(2)-bridged inter mediate 8(a) [PhL2 Pd <-- (OH)BR(9-BBN)]. This provides the precursor to transmetalation through a four-centered transition state 9. Because the analogous hydroxyborate complex is absent for 11, 14 is hydrolyze d by OH-1 forming 15 in a slower process, with this ultimately reactin g with 11 to form a related intermediate 8(b) [PhL2 Pd(OH) --> BR(OBBD )] which also collapses to products through 9.