Borane reagents

A. Pelter, K. Smith, and H. C. Brown, Borane Reagents, Academic Press, Inc., London, 1988. 

The milder metal hydnde reagents are also used in stereoselective reductions Inclusion complexes of amine-borane reagent with cyclodexnins reduce ketones to opucally active alcohols, sometimes in modest enantiomeric excess [59] (equation 48). Diisobutylaluminum hydride modified by zmc bromide-MMA. A -tetra-methylethylenediamme (TMEDA) reduces a,a-difluoro-[i-hydroxy ketones to give predominantly erythro-2,2-difluoro-l,3-diols [60] (equation 49). The three isomers are formed on reduction with aluminum isopropoxide... 

Since borane BH3 reacts with only one or two equivalents of a sterically hindered alkene, it is possible to prepare less reactive and more selective borane reagents R2BH and RBH2 respectively. In addition to disiamylborane 8 and thexylbo-rane 10, the 9-borabicyclo[3.3.1]nonane (9-BBN) 14 is an important reagent for hydroboration, since it is stable to air it is prepared by addition of borane 2 to cycloocta-1,5-diene 13 ... 

T. C. Chung, New utilities of metallocene catalysts and borane reagents in the functionalization and block/graft reactions of polyolefins, MetCon 95 Proceedings, USA, May 1995. 

For reviews, see Hoffmann, R.W. Niel, G. Schlapbach, A. Pure Appl. Chem., 1990, 62 1993 Pelter, A. Smith, K. Brown, H.C. Borane Reagents Academic Press NY, 1988, p 310. For a review of allylic boranes, see Bubnov, Yu.N. Pure Appl. Chem., 1987, 21, 89, For an example that proceeds with asymmetric induction, see Buynak, J.D. Geng, B Uang, S. Strickland, J.B. Tetrahedron Lett., 1994, 35, 985. 

Various metal complexes catalyze the addition of catecholborane and pinacolbo-rane to aliphatic terminal alkenes (Table 1-2). Neither the borane reagents nor the catalysts alter the high terminal selectivity, but a titanium catalyst does (entry 3). Although Cp2TiMe2 [30] exhibits high terminal selectivity for vinylarenes, aliphatic alkenes afford appreciable amounts of internal products, whereas an analogous Cp 2Sm(THF) [31] allows selective addition of catecholborane to the terminal car-... 

The dominant factors reversing the conventional ds-hydroboration to the trans-hydroboration are the use of alkyne in excess of catecholborane or pinacolborane and the presence of more than 1 equiv. of EtsN. The P-hydrogen in the ris-product unexpectedly does not derive from the borane reagents because a deuterium label at the terminal carbon selectively migrates to the P-carbon (Scheme 1-5). A vinylidene complex (17) [45] generated by the oxidative addition of the terminal C-H bond to the catalyst is proposed as a key intermediate of the formal trans-hydroboration. 

There is no systematic study of the effect of borane reagents, and the best choice would be highly dependent on the catalysts and substrates. A series of di(alkoxy)bo-ranes have recently been synthesized and subjected to hydroboration of cyclopen-tene at ambient temperature in the presence of RhCljPPhjjj (Scheme 1-2) [18]. The... 

TS, which is usually based on the chair (Zimmerman-Traxler) model. This pattern is particularly prevalent for the allylic borane reagents, where the Lewis acidity of boron promotes a tight cyclic TS, but at the same time limits the possibility of additional chelation. The dominant factors in these cases are the E- or Z-configuration of the allylic reagent and the conformational preferences of the reacting aldehyde (e.g., a Felkin-type preference.)... 

In Scheme 13.8, the side chain was added in one step by a borane carbonylation reaction. This synthesis is very short and the first four steps were used to transform the aldehyde group in the starting material to a methyl ester. The stereochemistry at C(4)-C(7) is established in the hydroboration in Step B, in which the C(7)-H bond is formed. A 1 1 mixture of diastereomers resulted, indicating that the configuration at C(4) has little influence on the direction of approach of the borane reagent. 

Devaky and Rajasree have reported the production of a polymer-bound ethylenediamine-borane reagent (63) (Fig. 41) for use as a reducing agent for the reduction of aldehydes.87 The polymeric reagent was derived from a Merrifield resin and a 1,6-hexanediol diacrylate-cross-linked polystyrene resin (HDODA-PS). The borane reagent was incorporated in the polymer support by complexation with sodium borohydride. When this reducing agent was used in the competitive reduction of a 1 1 molar mixture of benzaldehyde and acetophenone, benzaldehyde was found to be selectively reduced to benzyl alcohol. 

Figure 41 The polymer-bound ethylenediamine-borane reagent (63) for use as a reducing agent for the reduction of aldehydes. (Adapted from ref. 87.)...

The field of transition metal-catalyzed hydroboration has developed enormously over the last 20 years and is now one of the most powerful techniques for the transformation of C=C and C=C bonds.1-3 While hydroboration is possible in the absence of a metal catalyst, some of the more common borane reagents attached to heteroatom groups (e.g., catecholborane or HBcat, (1)) react only very slowly at room temperature (Scheme 1) addition of a metal catalyst M] accelerates the reaction. In addition, the ability to manipulate [M] through the judicious choice of ligands (both achiral and chiral) allows the regio-, chemo-, and enantioselectivity to be directed. 

The proposed mechanism starts with a methyl group abstraction on platinum complex 416 with the borane reagent in the presence of diyne 414 (Scheme 105). The square-planar cationic diyne-platinum(n) complex 417 is converted to the octahedral platinum(rv) hydride intermediate 418 through oxidative addition of the hydrosilane. This complex decomposes rapidly with methane release to form another tetracoordinated platinum(n) species 419, followed by platinasilylation of the triple bond. The resulting vinylplatinum 420 undergoes an intramolecular carboplatination to... 

Hydroboration, the addition of a boron-hydrogen bond across an unsaturated moiety, was first discovered by H. C. Brown in 1956. Usually, the reaction does not require a catalyst, and the borane reagent, most commonly diborane (B2H6) or a borane adduct (BH3-THF), reacts rapidly at room temperature to afford, after oxidation, the /AMarkovnikov alkene hydration product. However, when the boron of the hydroborating agent is bonded to heteroatoms which lower the electron deficiency, as is the case in catecholborane (1,3,2-benzodioxaborole) 1 (Scheme 1), elevated temperatures are needed for hydroboration to occur.4 5... 

In a soluble polymer strategy comparable to resin-capture [145], Janda reported a MeO-PEGsooo-supported dialkyl borane reagent (31) that was used in the purification of a solution-phase library of y9-amino alcohols [146]. Purification was achieved by simply adding (31) to the crude reaction mixture followed by subsequent precipitation of the polymer with diethyl ether to give polymer-supported 1,3,2-oxazaboroU-dine (32) (Scheme 5.2). The /9-amino alcohol product could then be released from the soluble support by treatment with acid. In a two-step synthetic strategy that is readily amendable to automation, the isolation of a small library of /9-amino alcohols was accomplished with all compounds obtained in >80% purity. 

In the hydroboration of terminal alkenes, carrying a ketone or aldehyde group, with a variety of borane reagents, dicyclohexylborane has been identified as the most efficient reagent. Analogous hydroboration of alkynyl ketones and alkynyl aldehydes with dicyclohexylborane yields the corresponding olefinic carbonyl compounds after protonation, or dicarbonyl compounds after oxidation. ... 

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