Methods for the synthesis of olefins and derivatives

A method of manufacturing an acrylate ester having the following formula

• wherein R represents straight or branched alkyl having 1 to 10 carbon atoms wherein said alkyl may be optionally and independently substituted with alkyl having 1 to 10 carbon atoms;
• phenyl;
• phenylalkyl;
• amino;
• hydroxy;
• alkylamino having 1 to 10 carbon atoms;
• and alkoxy having 1 to 10 carbon atoms or R represents cycloalkyl having 3 to 6 ring carbon atoms wherein said ring carbon atoms may be optionally and independently substituted with alkyl having 1 to 6 carbon atoms and hydroxy comprising reacting a fumarate diester having the following formula
• wherein R is defined as above with ethylene in the presence of a olefinic metathesis catalyst to produce the acrylate ester of formula III at about two moles of an acrylate ester per mole of fumarate diester.

A process for producing acrylic acid, comprising:

• (a) culturing in a sufficient amount of nutrients and media a non-naturally occurring microbial organism comprising a set of metabolic modifications obligatorily coupling fumaric acid production to growth of said microbial organism, said set of metabolic modifications comprising disruption of at least one of the gene sets comprising:
• (1) fumABC, zwf, purU, or
• (2) fumABC, zwf, glyA,
• or an ortholog thereof, to produce stable growth-coupled production of fumaric acid, and
• (b) contacting said fumaric acid with a sufficient amount of ethylene in the presence of a cross-metathesis transformation catalyst to produce about two moles of acrylic acid per mole of fumaric acid.

A process for producing an acrylate ester, comprising;

• (a) culturing in a sufficient amount of nutrients and media a non-naturally occurring microbial organism comprising a set of metabolic modifications obligatorily coupling fumaric acid production to growth of said microbial organism, said set of metabolic modifications comprising disruption of at least one of the gene sets comprising:
• (1) fumABC, zwf, purU, or
• (2) fumABC, zwf, glyA,
• or an ortholog thereof, to produce stable growth-coupled production of fumaric acid;
• (b) performing diesterification of said fumaric acid to produce fumarate diester, and
• (c) contacting said fumarate diester with a sufficient amount of ethylene in the presence of a cross-metathesis catalyst to produce about two moles of an acrylate ester per mole of fumarate diester.

An acrylic acid production system, comprising:

• (a) a culture of a non-naturally occurring microbial organism comprising a set of metabolic modifications obligatorily coupling fumaric acid production to growth of said microbial organism, said set of metabolic modifications comprising disruption of at least one of the gene sets comprising:
• (1) fumABC, zwf, purU, or
• (2) fumABC, zwf, glyA,
• or an ortholog thereof, which confer stable growth-coupled production of fumaric acid, and
• (b) an amount of ethylene and a cross-metathesis transformation catalyst sufficient to produce about two moles of acrylic acid per mole of fumaric acid.

An acrylate ester production system, comprising:

• (a) a culture of a non-naturally occurring microbial organism comprising a set of metabolic modifications obligatorily coupling fumaric acid production to growth of said microbial organism, said set of metabolic modifications comprising disruption of at least one of the gene sets comprising:
• (1) fumABC, zwf, purU, or
• (2) fumABC, zwf, glyA
• or an ortholog thereof, which confer stable growth-coupled production of fumaric acid;
• (b) at least one diesterification reagent sufficient to produce fumarate diester from said fumaric acid, and
• (c) an amount of ethylene and a cross-metathesis catalyst sufficient to produce about two moles of an acrylate ester per mole of fumarate diester.