多肽合成中困难序列的缩合研究进展(3)

时间:2025-03-10

非常详细的综述性文章

HANXiang,etal:Recent

progressintheimprovementofthecouplingefficiency

peptidesynthesis

of“difficultsequences’’in

’113

sequences”is

reversibleamide—backbonesubstitution.involvesN—substitution

of

one

leeular

reactive

acyltransfer

mechanism.Moreover

themore

Thisstrategy

ormore

or

Hnb(2一hydroxy-4一nitrobenzyl)

auxiliaries

have

been

uses

backbone

amidebondsofseveralresiduesbeforetheidentifiedexpected“difficult

sequences”in

protecting

introduced(Figure

nitrosame

peptide

is

to

31[13-.TheHnb

assist

auxillaryand

substituenttoadvantageous

sequences”.

encountered.Amide—backbonesubstitutionappears

prevent

or

acyltransfer

as

hasthe

disrupttroublesomeintermolecularhydrogen—

native

effectHmbfor

to

overcoming“difficult

bondingnetworksbythe

removaloftheamide

Compared

the

Hmbauxiliary,obviously

improved

hydrogenbondafterN—substitution,whichalterationofthebackboneconformationistionoftertiaryamidebonds.

The

solubility

improvement

is

attributed

to

acyltransferreactivity,especiallybranched

amino

acids,with

the

betweenlargeor卢一Hnbauxiliary

of

was

causedbytheintroduc—

obtained(Figure4).After

the

sequence,the

temporary

synthesisexpected

can

protectinggroupHnb

at

be

existenceoftertiaryamidebonds,X一(Z)Y,whereXandY

are

convenientlyremovedbymildphotolysisThe

oxidative—reductive

safety

catch

366nm[141.SiMb

arbitraryamino

acidresiduesandZis

(3一

temporary

causes

protectinggroup.The

of

tertiaryamide

structure

bondthethiscalled

methylsulfinyl-4一methoxy一6一hydroxybenzyl)backbone

auxiliaryalso

can

disturbanceof

tertiary

the卢一sheet

amide

bond

by

usedforthispurpose(Figure3)’15|.

rotation

plane

and

TheAib(o/。aminoisobutvricacid)residueusedin

peptidesynthesisisanothereffect.TheabilityofAibthe

solvation

of

to

case

segmentation“peptide

from卢一sheet

segment

structureswasthat

can

offerthePSS

separation

(PSS)”.Drab

is

promote

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