SELECTIVE CLEAVAGE OF THE ALLYL AND ALLYLOXCARBONYL GROUPS THROUGH PALLADIUM-CATALYZED HYDROSTANNOLYSIS WITH TRIBUTYLTIN HYDRIDE - APPLICATION TO THE SELECTIVE PROTECTION-DEPROTECTION OF AMINO-ACID DERIVATIVES AND IN PEPTIDE-SYNTHESIS
SELECTIVE CLEAVAGE OF THE ALLYL AND ALLYLOXCARBONYL GROUPS THROUGH PALLADIUM-CATALYZED HYDROSTANNOLYSIS WITH TRIBUTYLTIN HYDRIDE - APPLICATION TO THE SELECTIVE PROTECTION-DEPROTECTION OF AMINO-ACID DERIVATIVES AND IN PEPTIDE-SYNTHESIS
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DOI：
10.1021/jo00231a027
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发表时间：
1987-10-30
影响因子：
3.6
通讯作者：
MARQUET, A
中科院分区：
文献类型：
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作者：
DANGLES, O;GUIBE, F;MARQUET, A
在质子供体(冰醋酸、对-硝基苯酚、乙酸吡啶、水)存在下，钯催化氢化锡氢化物与三丁基锡氢化物反应，可将胺和氨基酸的N-烯丙氧基酮基衍生物快速定量地转化为游离氨基酸化合物。类似的程序可用于去保护烯丙基(ALL)羧酸盐和烯丙基芳基醚。对N-Alc和O-Bzl、N-Z和O-All、N-Alc和O-t-Bu以及N-Alc和N-Boc保护的氨基酸衍生物进行了脱保护实验。钯催化的氢化锡解裂解与Bzl和Z保护基团完全相容；此外，BOC和t-Bu基团以及Alalc和所有基团似乎是正交的。通过固相合成具有生物活性的十一肽物质P，说明了ALLOC方法用于暂时保护α-氨基功能的可靠性。
N-Allyloxycarbonyl (Alloc) derivaties of amines and amino acids are quantitatively and very rapidly converted to free amino compounds by palladium-catalyzed hydrostannolytic cleavage with tributyltin hydride in the presence of a proton donor (acetic acid, p-nitrophenol, pyridinium acetate, water). A similar procedure can be used for the deprotection of allyl (All) carboxylates and allyl aryl ethers. Deprotection experiments were performed on various mixed N-Alloc and O-Bzl, N-Z and O-All, N-Alloc and O-t-Bu, and N-alloc- and N-Boc-protected amino acid derivatives. The palladium-catalyzed hydrostannolytic cleavage is fully compatible with the Bzl and Z protecting groups; furthermore the BOC and t-Bu groups and the Alloc and All groups appear to be orthogonal. The reliability of the Alloc methodology for temporary protection of the .alpha.-amino functions is illustrated by the solid-phase synthesis of the biologically active undecapeptide substance P.