Tulathromycin Synthesis via Selective Oxidation

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Solution Overview

Problem

Existing methods for preparing tulathromycin require protection and deprotection of functional groups, leading to increased time, cost, and yield reduction due to additional steps, hazardous reagents, and side reactions, resulting in impurities and waste.

Innovation Solution

A process that directly converts compound of formula (I) to compound of formula (II) without protecting the C-2' hydroxyl group, using an oxidation reaction with dimethyl sulfoxide (DMSO) and trifluoroacetic anhydride in the presence of triethylamine, simplifying the process and reducing the need for hazardous reagents.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If protection and deprotection steps are added to prepare compound of formula (II), then the oxidation reaction can proceed, but the process time increases and yield decreases

Engineering Contradiction:
Improveoxidation reaction successVSAvoidprocess time
Core Design Contradiction:
ReliabilityVSLoss of time

Solution Approach 1:

The invention extracts and removes the unnecessary protection and deprotection steps from the synthesis pathway. By using selective oxidation conditions (oxalyl chloride/DMSO system) that specifically target the C-4'' hydroxyl group, the method eliminates the need for protecting group chemistry, directly converting compound of formula (I) to compound of formula (II) in a single oxidation step without additional time-consuming deprotection operations.

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

The invention performs preliminary selective protection of the C-4'' hydroxyl group through the oxidation mechanism itself. The oxalyl chloride/DMSO system selectively activates and oxidizes the C-4'' hydroxyl group while leaving other hydroxyl groups (C-2', C-3', C-9a) untouched, effectively achieving protection of the reactive site before the main oxidation reaction occurs, thus preventing side reactions without requiring external protecting groups.

Inventive Principle:
Principle #10Preliminary action

2Reliability

If protection and deprotection steps are added to prepare compound of formula (II), then the oxidation reaction can proceed, but the manufacturing cost increases

Engineering Contradiction:
Improveoxidation reaction successVSAvoidmanufacturing cost
Core Design Contradiction:
ReliabilityVSEase of manufacture

Solution Approach 1:

The invention extracts and eliminates the expensive protection and deprotection steps from the synthesis pathway. By using selective oxidation conditions (oxalyl chloride/DMSO system) that specifically target the C-4'' hydroxyl group, the method removes the need for costly protecting group reagents (such as benzylchloroformate, acetic anhydride) and additional purification operations, directly converting compound of formula (I) to compound of formula (II) in a single oxidation step.

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

The invention replaces expensive, multi-step protection chemistry with a cheap, single-step oxidation system using oxalyl chloride and DMSO. These reagents are inexpensive, readily available, and perform their function in a single use without requiring recovery or complex disposal procedures associated with traditional protecting groups like benzyl chloroformate or acetyl groups.

Inventive Principle:
Principle #27Cheap short-living objects (Disposable)

3Reliability

If protection and deprotection steps are added to prepare compound of formula (II), then the oxidation reaction can proceed, but the yield decreases due to additional steps and side reactions

Engineering Contradiction:
Improveoxidation reaction successVSAvoidyield
Core Design Contradiction:
ReliabilityVSProductivity

Solution Approach 1:

The invention performs preliminary selective protection of the C-4'' hydroxyl group through the oxidation mechanism itself. The oxalyl chloride/DMSO system selectively activates and oxidizes the C-4'' hydroxyl group while leaving other hydroxyl groups (C-2', C-3', C-9a) untouched, effectively achieving protection of the reactive site before the main oxidation reaction occurs, thus preventing side reactions without requiring external protecting groups.

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The invention converts the potential harm of multiple reactive hydroxyl groups (which could lead to side reactions and impurities) into a benefit by using the selective oxidation conditions to specifically target and differentiate between the C-4'' hydroxyl group and other hydroxyl groups. The presence of multiple hydroxyl groups, which would normally require protection to prevent side reactions, becomes advantageous as the selective reagent can distinguish and oxidize only the C-4'' position, improving overall yield and reducing impurity formation.

Inventive Principle:
Principle #22Blessing in disguise (Convert harm into benefit)

4Reliability

If protection and deprotection steps are added to prepare compound of formula (II), then the oxidation reaction can proceed, but harmful reagents and hazardous conditions are required

Engineering Contradiction:
Improveoxidation reaction successVSAvoidhazardous reagents
Core Design Contradiction:
ReliabilityVSObject-affected harmful factors

Solution Approach 1:

The invention extracts and removes the harmful protection and deprotection steps from the synthesis pathway. By using selective oxidation conditions (oxalyl chloride/DMSO system) that specifically target the C-4'' hydroxyl group, the method eliminates the need for hazardous protecting group reagents (such as benzylchloroformate requiring hydrogenation with Pd/C, or other harsh deprotection conditions), directly converting compound of formula (I) to compound of formula (II) in a single oxidation step without additional hazardous operations.

Inventive Principle:
Principle #2Taking out (Extraction)

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 reduces the complexity and cost of the process, increases yield, and minimizes impurities by eliminating the need for protection and deprotection steps, while maintaining high purity and efficiency in the production of tulathromycin intermediates.

Implementation Method 1

the C-4'' hydroxyl group of the compound of formula (I) to form the compound of formula (A)

Methodology Applied
Scientific EffectOxidation: Oxidation

Implementation Method 2

in the presence of triethylamine

Methodology Applied
Scientific EffectBase-neutralization reaction: Chemical Bonding

Data Source

PatentEP3027634B1Process for preparation of tulathromycin
Publication Date: 2018.03.21 FARMA GRS D O O
  • EP3027634B1 patent drawingFigure 1
  • EP3027634B1 patent drawingFigure 2
  • EP3027634B1 patent drawingFigure 3

AI summary

The present invention discloses a novel process for preparation of tulathromycin. The process uses fewer steps due to a more direct route without prior protection of functional groups of the compound of formula (I).