Tris silane with primary amines

Both compounds 5 and 8 readily react with primary amines giving the corresponding tris(amino-silyl)methanes and -silanes (Scheme 2). 

The combination of PhSiH3 with a catalytic amount of bis(tri-n-butyltin) oxide reduces azides to primary amines in excellent yields (Eq. 3 33).556 The reducing agent is (n-Bu)3SnH formed in situ by the silane. Azides are converted into Boc-protected primary amines with the PMHS/Pd/C reagent (Eq. 3 34).557,558... 

JL olysilazanes have now been prepared by the catalyzed transamination of HSi[N(CH3)2]3 [tris(dimethylamino)silane, Tris], or its derivatives, with ammonia, primary amines, hydrazines, or diamines. Chlorosilane intermediates are not required in this process, because Tris is readily prepared in excellent yield via a new direct reaction of silicon with dimethylamine. 

A further valuable tool in organic chemistry is facilitated by isocyanides the deamination reaction. When the standard deamination reaction via a diazonium salt is undesirable (due to a need to avoid acidic conditions), primary amines can be converted by well-known methods into isocyanides, which are reduced using tri-butyltin hydride under Bartorf s conditions (heating for 5 h at 80 °C in toluene). This reaction sequence has been applied as a new route to 1,3-polyols using azetidinone frameworks 1565 as chiral templates [1188]. Dehydration of the formamide 1567 was accomplished with triphosgene to afford the isocyanide 1568, which was reduced efficiently with tris(trimethylsilyl)silane to afford the desired a,y-dialkoxy ester 1569 in 80% yield [1188]. 

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