Tungsten Oxometallacyclobutane Z-Selective Metathesis Catalyst

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Solution Overview

Problem

There is a need for improved methods and catalysts in olefin metathesis reactions, particularly for achieving Z selective couplings of terminal olefins, as existing tungsten oxo alkylidene complexes have limited activity and selectivity.

Innovation Solution

Development of tungsten oxo alkylidene complexes with specific ligands, such as O-2,6-(2,4,6-triisopropylphenyl) 2 C 6 H 3 (OHIPT), that promote Z selective metathesis reactions by forcing metallacyclobutane substituents to one side of the ring, allowing only Z products to form, and exploration of MAP (monoaryloxide monopyrrolide) complexes for enhanced catalytic activity.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If conventional tungsten oxo alkylidene complexes are used, then the metathesis reaction can proceed, but the catalytic activity is low and Z selectivity is poor

Engineering Contradiction:
Improvecatalytic activityVSAvoidZ selectivity
Core Design Contradiction:
ProductivityVSManufacturing precision

Solution Approach 1:

The patent changes the chemical parameters of the catalyst by introducing specific ligands (MAP ligands with bulky aryl groups and electron-withdrawing substituents) to modify the electronic and steric properties of the tungsten center, thereby improving both catalytic activity and Z selectivity

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent employs asymmetric ligand design where the MAP ligand creates a chiral environment at the metal center, inducing Z selectivity through steric constraints that force metallacyclobutane substituents to one side of the ring

Inventive Principle:
Principle #4Asymmetry

2Manufacturing precision

If existing catalyst systems are used for terminal olefin metathesis, then the reaction occurs, but the Z:E isomer ratio is not sufficiently high

Engineering Contradiction:
ImproveZ:E isomer ratioVSAvoidreaction efficiency
Core Design Contradiction:
Manufacturing precisionVSProductivity

Solution Approach 1:

The patent applies local quality by introducing specific functional groups (electron-withdrawing substituents like CF3, F, or Cl) at specific positions on the ligand structure to create localized electronic effects that enhance Z selectivity without compromising overall catalytic activity

Inventive Principle:
Principle #3Local quality

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

The proposed complexes demonstrate improved catalytic activity and selectivity for Z selective metathesis reactions, achieving high enantioselectivity and Z:E isomer ratios, making them suitable for efficient olefin metathesis processes.

Implementation Method 1

Catalytic olefin metathesis has transformed chemical synthesis and offers exceptionally efficient pathways for synthesis of alkenes

Methodology Applied
Scientific EffectCatalysis: Catalysis

Data Source

PatentEP2780349B1Tungsten oxo alkylidene complexes for z selective olefin metathesis
Publication Date: 2019.02.27 MASSACHUSETTS INST OF TECH
  • EP2780349B1 patent drawingFigure 1
  • EP2780349B1 patent drawingFigure 2
  • EP2780349B1 patent drawingFigure 3

AI summary

The current application describes tungsten oxo alkylidene complexes for olefin metathesis.