TY - JOUR
T1 - Synthesis and Structure of Cellular Mediators
T2 - Inositol Polyphosphate Diphosphates
AU - Falck, J. R.
AU - Reddy, K. Kishta
AU - Ye, Jianhua
AU - Saady, Mourad
AU - Mioskowski, Charles
AU - Shears, Stephen B.
AU - Tan, Zheng
AU - Safrany, Stephen
PY - 1995/1/1
Y1 - 1995/1/1
N2 - The first total syntheses of 1-O-[(phosphonooxy)hydroxyphosphinyl]-2,3,4,5,6-pentakis-O-phosphono-D-myoinositol (10) and its antipode (11) were achieved from enantiopure 2,3:5,6-di-O-cyclohexylidene-D-myo-inositol (6). The critical pyrophosphate function was introduced, in the presence of flanking phosphate triesters, by mild LiCN-mediated cleavage of a mixed phosphate methyl ester, isolation of the resultant lithium salt, and addition to dibenzyl chlorophosphonate. The benzyl esters were removed by catalytic hydrogenolysis over Pd in t-BuOH/H2O in the presence of NaHCO3. Comparisons of synthetic and enzyme-devived pyrophosphates with two phosphatases suggests natural material has the stereochemical configuration in 10.
AB - The first total syntheses of 1-O-[(phosphonooxy)hydroxyphosphinyl]-2,3,4,5,6-pentakis-O-phosphono-D-myoinositol (10) and its antipode (11) were achieved from enantiopure 2,3:5,6-di-O-cyclohexylidene-D-myo-inositol (6). The critical pyrophosphate function was introduced, in the presence of flanking phosphate triesters, by mild LiCN-mediated cleavage of a mixed phosphate methyl ester, isolation of the resultant lithium salt, and addition to dibenzyl chlorophosphonate. The benzyl esters were removed by catalytic hydrogenolysis over Pd in t-BuOH/H2O in the presence of NaHCO3. Comparisons of synthetic and enzyme-devived pyrophosphates with two phosphatases suggests natural material has the stereochemical configuration in 10.
UR - http://www.scopus.com/inward/record.url?scp=0029564411&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0029564411&partnerID=8YFLogxK
U2 - 10.1021/ja00154a017
DO - 10.1021/ja00154a017
M3 - Article
AN - SCOPUS:0029564411
SN - 0002-7863
VL - 117
SP - 12172
EP - 12175
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 49
ER -