Phenacyl-Protected Sialic Acid in Boc Solid Phase Synthesis

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Solution Overview

Problem

The existing solid phase synthesis methods, particularly those using the Boc group, face challenges in retaining sialic acid at the sugar chain non-reducing terminal due to strong acid conditions, leading to degradation and low yields of glycopeptides with sialyl sugar chains.

Innovation Solution

The use of a phenacyl group as a protecting agent for the carboxyl group of sialic acid in the Boc solid phase synthesis method, combined with specific acid conditions like trifluoroacetic acid/trifluoromethanesulfonic acid/dimethyl sulfide/m-cresol, allows for the retention of sialic acid and improved yield of glycopeptides with sialyl sugar chains.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If Boc solid phase synthesis method is used, then peptide chain elongation can proceed efficiently, but sialic acid at the sugar chain non-reducing terminal is degraded due to strong acid conditions

Engineering Contradiction:
Improvepeptide chain elongation efficiencyVSAvoidsialic acid retention
Core Design Contradiction:
ProductivityVSReliability

Solution Approach 1:

The phenacyl group is introduced as a protecting group for the carboxyl group of sialic acid before the Boc solid phase synthesis process. This preliminary protection prevents the degradation of sialic acid during the subsequent strong acid treatment, allowing the peptide chain elongation to proceed efficiently while maintaining sialic acid integrity.

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The phenacyl group acts as an intermediary protecting group that mediates between the strong acid conditions required for Boc deprotection and the sensitivity of sialic acid. This intermediary structure allows the strong acid to access the peptide backbone without directly attacking the sialic acid, thus enabling both efficient synthesis and high retention.

Inventive Principle:
Principle #24Intermediary (Mediator)

2Ease of manufacture

If conventional protecting groups are used for sialic acid, then synthesis can proceed, but yield remains low due to insufficient retention of sialic acid

Engineering Contradiction:
Improvesynthesis feasibilityVSAvoidglycopeptide yield
Core Design Contradiction:
Ease of manufactureVSProductivity

Solution Approach 1:

The invention changes the protecting group parameter from conventional groups (such as methyl or benzyl) to the phenacyl group. This parameter change provides optimal protection against acid-mediated degradation while maintaining compatibility with the Boc solid phase synthesis conditions, thereby significantly improving the yield of glycopeptides with sialyl sugar chains.

Inventive Principle:
Principle #35Parameter changes

3Ease of operation

If strong acid is used for deprotection and cleavage, then peptide can be released from resin, but sialic acid structure is compromised

Engineering Contradiction:
Improvedeprotection and cleavage efficiencyVSAvoidsialic acid structural integrity
Core Design Contradiction:
Ease of operationVSManufacturing precision

Solution Approach 1:

The phenacyl protecting group is installed on the sialic acid carboxyl group before the deprotection and cleavage steps. This preliminary protection ensures that when strong acid is applied for Boc group removal and peptide release, the sialic acid structure remains intact while the peptide is successfully liberated from the resin.

Inventive Principle:
Principle #10Preliminary action

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

This approach enables the high-yield synthesis of glycopeptides with sialyl sugar chains, maintaining the integrity of sialic acid and allowing for the production of glycopeptides with uniform sugar chain structures suitable for pharmaceutical applications.

Implementation Method 1

the carboxyl group of said sialic acid is protected with a phenacyl group

Methodology Applied
Scientific EffectProtecting group chemistry:

Implementation Method 2

specific acid conditions like trifluoroacetic acid/trifluoromethanesulfonic acid/dimethyl sulfide/m-cresol

Methodology Applied
Scientific EffectAcid hydrolysis: Hydrolysis

Data Source

PatentEP2684899B1Method for producing glycopeptide having sialyl sugar chain, sialyl sugar chain-added amino acid derivative to be used in same, and glycopeptide
Publication Date: 2018.04.25 GLYTECH LLC
  • EP2684899B1 patent drawingFigure 1
  • EP2684899B1 patent drawingFigure 2
  • EP2684899B1 patent drawingFigure 3

AI summary

[Technical Promblem] To provide a method for manufacturing that enables to obtain a targeted glycopeptide harboring a sialyl sugar chain in high yield without decomposing sialic acid at a non-reducing terminal of sugar chain when the glycopeptide is synthesized by a Boc solid phase synthesis method. [Solution to Problem] The present invention is characterized in that the Boc-sialylglycosylated amino acid derivative used in Boc solid phase synthesis method is one where the carboxyl group of the sialic acid at the sugar chain non-reducing terminal is protected with a phenacyl group.