Further characterization of Mitsunobu-type intermediates in the reaction of dialkyl azodicarboxylates with P(III) compounds.
Structural characterization of compounds analogous to the proposed intermediates in the Mitsunobu esterification process is achieved by the combined use of NMR spectroscopy and X-ray diffractometric studies. The results show that compounds (t-BuNH)P(mu-N-t-Bu)(2)P[(N-t-Bu)(N-(CO(2)R)-N(H)(CO(2)R))] [R = Et (11), i-Pr (12)], obtained by treating [(t-Bu-NH)P-mu-N-t-Bu](2) (10) with diethylazodicarboxylate (DEAD) or diisopropylazodicarboxylate (DIAD), respectively, have a structure with the NH proton residing between the two nitrogen atoms ((P)N(t-Bu) and (P)N-N(CO(2)Et)); this is the tautomeric form of the expected betaine (t-BuNH)P(mu-N-t-Bu)(2)P(+)[(NH-t-Bu)(N-(CO(2)R)-N(-)(CO(2)R)]. Treatment of ClP(mu-N-t-Bu)(2)P[(N-t-Bu){N-(CO(2)-i-Pr)-N(H)(CO(2)-i-Pr)] (6) with 2,6-dicholorophenol affords (2,6-Cl(2)-C(6)H(3)-O)P(mu-N-t-Bu)(2)P(+)[(NH-t-Bu){N[(CO(2)i-Pr)(HNCO(2)i-Pr)]}](Cl(-))(2,6-Cl(2)-C(6)H(3)-OH) (14) that has a structure similar to that of (CF(3)CH(2)O)P(mu-N-t-Bu)(2)P(+)[(NH-t-Bu){N[(CO(2)i-Pr)(HNCO(2)i-Pr)]}](Cl(-)) (13), but with an additional hydrogen bonded phenol. Both of these have the protonated betaine structure analogous to that of Ph(3)P(+)N(CO(2)R)NH(CO(2)R)(R'CO(2))(-) (2) proposed in the Mitsunobu esterification. Two other compounds, (ArO)P(mu-N-t-Bu)(2)P(+)(NH-t-Bu){N(CO(2)i-Pr)(HNCO(2)i-Pr)}(Cl(-)) [Ar = 2,6-Me(2)C(6)H(3)O- (15) and 2-Me-6-t-Bu-C(6)H(3)-O- (16)], are also prepared by the same route. Although NMR tube reactions of 11 or 12 with tetrachlorocatechol, catechol, 2,2'-biphenol, and phenol revealed significant changes in the (31)P NMR spectra, attempted isolation of these products was not successful. On the basis of (31)P NMR spectra, the phosphonium salt structure (t-BuNH)P(mu-N-t-Bu)(2)P(+)[(HN-t-Bu){N-(CO(2)R)-N(H)(CO(2)R)](ArO(-)) is proposed for these. The weakly acidic propan-2-ol or water did not react with 11 or 12. Treatment of 12 with carboxylic acids/ p-toluenesulfonic acid gave the products (t-BuNH)P(mu-N-t-Bu)(2)P(+)[(HN-t-Bu){N-(CO(2)-i-Pr)-N(H)(CO(2)-i-Pr)](ArCO(2)(-)) [Ar = Ph (18), 4-Cl-C(6)H(4)CH(2) (19), 4-Br-C(6)H(4) (20), 4-NO(2)-C(6)H(4) (21)] and (t-BuNH)P(mu-N-t-Bu)(2)P(+)[(HN-t-Bu){N-(CO(2)-i-Pr)-N(H)(CO(2)-i-Pr)](4-CH(3)-C(6)H(4)SO(3)(-)) (22) that have essentially the same structure as 2. Compound 18 has additional stabilization by hydrogen bonding, as revealed by X-ray structure determination. Finally it is shown that the in situ generated (t-BuNH)P(mu-N-t-Bu)(2)P(+)[(HN-t-Bu){N-(CO(2)Et)-N(H)(CO(2)Et)](4-NO(2)-C(6)H(4)CO(2)(-)) can also effect Mitsunobu esterification. A comparison of the Ph(3)P-DIAD system with the analogous synthetically useful Ph(3)P-dimethyl acetylenedicarboxylate (DMAD) system is made.
Swamy
K C Kumara
KC
School of Chemistry, University of Hyderabad, Hyderabad 500 046, A. P., India. kckssc@uohyd.ernet.in
Kumar
K Praveen
KP
Kumar
N N Bhuvan
NN