NOVEL HIGH-YIELD TRANSESTERIFICATION AND TRANSAMINATION ROUTES TO P(OCH₂)₃CCH₃AND P[N(CH₃)CH₂]₃CCH₃, RESPECTIVELY

Comparisons of Phosphorus Ligation Properties in P(CH2NR)3P

“…IR and NMR Spectroscopic Studies of 8a − f. The 31 P NMR spectrum of the mixture of P(CH 2 NHMe) 3 and aminophosphine oligomers showed a broad peak at −59.9 ppm which is in the expected range for compounds of the type P(CH 2 NH−) 3 . ,, The 31 P NMR spectrum of 8a displayed an AM pattern consisting of a pair of doublets due to mutual coupling of the two chemically different phosphorus atoms. 6c, The 31 P chemical shift for the PN 3 phosphorus in 8a (82.3 ppm) is upfield relative to that for P(NMe 2 ) 3 (δ P 123.0 ppm). We are unable to associate this upfield shift with a significant change in the average NPN angle in 8a {which is probably close to those in 9a [99.30(6)°] and 8b [101.31(8)°] (see below)} relative to that in P(NMe 2 ) 3 [average NPN angle = 102.0(2)°].…”

“…All reactions were carried out under argon. Solvents were purified by standard procedures prior to use, and the following compounds were prepared by published methods: (η 5 -C 5 Me 5 )RuCl(COD), 3a ,6a and 9a ,6c as well as P(CH 2 NHPh) 3 24 that was used to prepare 9a . [P(CH 2 OH) 4 ] 2 SO 4 (a generous donation from Albright & Wilson, Americas), BH 3 ·THF, 9-BBN, and Mo(CO) 4 (NBD) (Aldrich), and W(CO) 6 and Mo(CO) 3 (CHT) (Strem) were used as received.…”

“…Bicyclic 2 as well as its perfluoro and perchloro aromatic analogues have been reported, and the dioxide5a and protonated form 5b of perhydro 2 are also known. In 1965 our group and others reported various syntheses of 3a . Although phosphines are usually considered to be more Lewis basic than phosphites, the PO 3 phosphorusof 3a was shown to react preferentially with chalcogens and transition metals, and evidence consistent with better π-acceptor properties of the PO 3 phosphorus was presented. 6a,− A variety of nonmetal derivatives ( 3b − k ) and transition metal complexes ( 3l − x ) of 3a have appeared in the literature. 6a,− R groups other than H in 3a (i.e., 4 − 7 ), halo derivatives P(RCHO) 3 PX 2 of 4 − 6 , oxo derivatives P[C(R)HO] 3 PO and OP[C(CCl 3 )HO] 3 P of 4 − 6 , and P[C(CCl 3 )HO] 3 P=NTs have also been synthesized. −

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“…Compounds 8a and 9a 17 have been reported by us, as has been an improved route to 9a 6c. A multistep synthesis of 10 has been described, and bicyclic diphosphines bearing N−N ( 11 19 ), Si−Si ( 12 20 ), or Sn−Sn ( 13 21 ) linkages are known.…”