Methods for the synthesis of olefins and derivatives

1. A process for producing acrylic acid, comprising:

(a) culturing in a sufficient amount of nutrients and media a non-naturally occurring Escherichia coli bacterium comprising a set of metabolic modifications obligatorily coupling fumaric acid production to growth of said Escherichia coli bacterium, 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.

2. The process of claim 1 , wherein said set of metabolic modifications comprises disruption of at least one of the gene sets comprising:

(1) fumABC, zwf, purU, or

(2) fumABC, zwf, glyA,

or an ortholog thereof, and wherein said genes encoding said metabolic modifications (1) fumABC, zwf, purU further comprises disruption of at least one gene selected from ackA-pta, gdhA, pntAB or ackA-pta, yibO, ythE.

3. The process of claim 2 , wherein said disruption comprises a deletion of at least one gene within said gene set.

4. The process of claim 1 , wherein said nutrients and media comprise at least one carbon substrate selected from glucose, sucrose, xylose, arabinose, galactose, mannose and fructose.

5. The method of claim 1 , wherein said cross-metathesis transformation catalyst is a ruthenium catalyst bearing an N-heterocyclic carbene ligand.

6. The method of claim 1 , wherein said cross-metathesis transformation catalyst is a ruthenium catalyst and said rhuthenium catalyst comprises Cl 2 (PCy 3 ) 2 Ru═CHPh or the phosphine-free carbene ruthenium catalyst [1,3-bis(2,6-dimethylphenyl)4,5-dihydroimidazol-2-ylidene](C 5 H 5 N) 2 (Cl) 2 Ru═CHPh.

7. An acrylic acid production system, comprising:

(a) a culture of a non-naturally occurring Escherichia coli bacterium comprising a set of metabolic modifications obligatorily coupling fumaric acid production to growth of said Escherichia coli bacterium, 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.

8. The production system of claim 7 , wherein said genes encoding said metabolic modifications (1) fumABC, zwf, purU further comprises disruption of at least one gene selected from ackA-pta, gdhA, pntAB or ackA-pta, yibO, ythE.

9. The production system of claim 7 , wherein said disruption comprises a deletion of at least one gene within said gene set.

10. The production system of claim 7 , wherein said nutrients and media comprise at least one carbon substrate selected from glucose, sucrose, xylose, arabinose, galactose, mannose and fructose.

11. The method of claim 7 , wherein said cross-metathesis transformation catalyst is ruthenium catalyst bearing an N-heterocyclic carbene ligand.

12. The method of claim 7 , wherein said cross-metathesis transformation catalyst is a ruthenium catalyst and said rhuthenium catalyst comprises Cl 2 (PCy 3 ) 2 Ru═CHPh or the phosphine-free carbene ruthenium catalyst [1,3-bis(2,6-dimethylphenyl)4,5-dihydroimidazol-2-ylidene](C 5 H 5 N) 2 (Cl) 2 Ru═CHPh.

13. A process comprising:

(a) culturing by fermentation in a sufficient amount of nutrients and media a non-naturally occurring Escherichia coli bacterium that produces fumaric acid; and

(b) performing a chemical modification comprising metathesis with ethylene to convert fumaric acid to acrylic acid.

14. The process of claim 13 further comprising:

(c) contacting said acrylic acid with a sufficient amount of a disubstitued alkene in the presence of an olefin metathesis transformation catalyst to produce a second, different olefin.