MICROORGANISMS AND METHODS FOR THE PRODUCTION OF CAPROLACTONE

1 . A non-naturally occurring microbial organism, said microbial organism having a caprolactone pathway and comprising at least one exogenous nucleic acid encoding a caprolactone pathway enzyme expressed in a sufficient amount to produce caprolactone, wherein said caprolactone pathway comprises a pathway selected from:

(1) 1D, 1A, 1B, and 1C;

(2) 1E, 1B, 1C and 1D;

(3) 1F, 1A, 1B, 1C and 1D;

(4) 1F, 1E, 1B, 1C and 1D;

(5) 1A, 1B and 1G;

(6) 1E, 1B and 1G;

(7) 1F, 1A, 1B and 1G;

(8) 1F, 1E, 1B and 1G;

(9) 1A, 1B, 1C, 1J and 1I;

(10) 1E, 1B, 1C, 1J and 1I;

(11) 1F, 1A, 1B, 1C, 1J and 1I;

(12) 1F, 1E, 1B, 1C, 1J and 1I;

(13) 1A, 1B, 1H and 1I;

(14) 1E, 1B, 1H and 1I;

(15) 1F, 1A, 1B, 1H and 1I;

(16) 1F, 1E, 1B, 1H and 1I;

(17) 2A, 2B, 2C, 2D, 2E and 2F;

(18) 2A, 2B, 2C, 2D and 2G;

(19) 2A, 2B, 2C, 2D, 2E, 2J and 2I;

(20) 2A, 2B, 2C, 2D, 2H and 2I;

(21) 4A, 4B, 4C, 4D and 3A; and

(22) 5A, 5B, 5C an 3A,

wherein 1A is an adipyl-CoA reductase, wherein 1B is an adipate semialdehyde reductase, wherein 1C is a 6-hydroxyhexanoyl-CoA transferase or a 6-hydroxyhexanoyl-CoA synthetase, wherein 1D is a 6-hydroxyhexanoyl-CoA cyclase or spontaneous cyclization, wherein 1E is an adipate reductase, wherein 1F is an adipyl-CoA transferase, an adipyl-CoA synthetase or an adipyl-CoA hydrolase, wherein 1G is a 6-hydroxyhexanoate cyclase, wherein 1H is a 6-hydroxyhexanoate kinase, wherein 11 is a 6-hydroxyhexanoyl phosphate cyclase or spontaneous cyclization, wherein 1J is a phosphotrans-6-hydroxyhexanoylase, wherein 2A is a 4-hydroxybutyryl-CoA:acetyl-CoA acyltransferase, wherein 2B is a 3-oxo-6-hydroxyhexanoyl-CoA reductase, wherein 2C is a 3,6-dihydroxyhexanoyl-CoA dehydratase, wherein 2D is a 6-hydroxyhex-2-enoyl-CoA reductase, wherein 2E is a 6-hydroxyhexanoyl-CoA transferase, a 6-hydroxyhexanoyl-CoA synthetase or a 6-hydroxyhexanoyl-CoA hydrolase, wherein 2F is a 6-hydroxyhexanoate cyclase, wherein 2G is a 6-hydroxyhexanoyl-CoA cyclase or spontaneous cyclization, wherein 2H is a phosphotrans-6-hydroxyhexanoylase, wherein 2I is a 6-hydroxyhexanoyl phosphate cyclase or spontaneous cyclization, wherein 2J is a 6-hydroxyhexanoate kinase, wherein 3A is a cyclohexanone monooxygenase, wherein 4A is an adipate semialdehyde dehydratase, wherein 4B is a cyclohexane-1,2-dione reductase, wherein 4C is a 2-hydroxycyclohexanone reductase, wherein 4D is a cyclohexane-1,2-diol dehydratase, wherein 5A is a 2-ketocyclohexane-1-carboxoyl-CoA hydrolase (acting on C—C), wherein 5B is a 2-ketocyclohexane-1-carboxoyl-CoA transferase, a 2-ketocyclohexane-1-carboxoyl-CoA synthetase or a 2-ketocyclohexane-1-carboxoyl-CoA hydrolase, and wherein 5C is a 2-ketocyclohexane-1-carboxylate decarboxylase.

2 . The non-naturally occurring microbial organism of claim 1 , wherein said microbial organism comprises two, three, four, five, six or seven exogenous nucleic acids each encoding a caprolactone pathway enzyme.

3 . The non-naturally occurring microbial organism of claim 2 , wherein said microbial organism comprises exogenous nucleic acids encoding each of the enzymes of at least one of the pathways selected from (1)-(22).

4 . The non-naturally occurring microbial organism of claim 1 , wherein said at least one exogenous nucleic acid is a heterologous nucleic acid.

5 . The non-naturally occurring microbial organism of claim 1 , wherein said non-naturally occurring microbial organism is in a substantially anaerobic culture medium.

6 . The non-naturally occurring microbial organism of claim 1 , further comprising:

(i) a reductive TCA pathway comprising at least one exogenous nucleic acid encoding a reductive TCA pathway enzyme, wherein said at least one exogenous nucleic acid is selected from an ATP-citrate lyase, citrate lyase, a citryl-CoA synthetase, a citryl-CoA, a fumarate reductase, and an alpha-ketoglutarate:ferredoxin oxidoreductase;

(ii) a reductive TCA pathway comprising at least one exogenous nucleic acid encoding a reductive TCA pathway enzyme, wherein said at least one exogenous nucleic acid is selected from a pyruvate:ferredoxin oxidoreductase, a phosphoenolpyruvate carboxylase, a phosphoenolpyruvate carboxykinase, a CO dehydrogenase, and an H 2 hydrogenase; or

(iii) at least one exogenous nucleic acid encodes an enzyme selected from a CO dehydrogenase, an H 2 hydrogenase, and combinations thereof.

7 . The non-naturally occurring microbial organism of claim 5 , wherein said microbial organism comprising (i) further comprises an exogenous nucleic acid encoding an enzyme selected from a pyruvate:ferredoxin oxidoreductase, an aconitase, an isocitrate dehydrogenase, a succinyl-CoA synthetase, a succinyl-CoA transferase, a fumarase, a malate dehydrogenase, an acetate kinase, a phosphotransacetylase, an acetyl-CoA synthetase, an NAD(P)H:ferredoxin oxidoreductase, ferredoxin, and combinations thereof.

8 . The non-naturally occurring microbial organism of claim 5 , wherein said microbial organism comprising (ii) further comprises an exogenous nucleic acid encoding an enzyme selected from an aconitase, an isocitrate dehydrogenase, a succinyl-CoA synthetase, a succinyl-CoA transferase, a fumarase, a malate dehydrogenase, and combinations thereof.

9 . The non-naturally occurring microbial organism of claim 5 , wherein said microbial organism comprising (i) comprises three exogenous nucleic acids encoding an ATP-citrate lyase or a citrate lyase, a fumarate reductase, and an alpha-ketoglutarate:ferredoxin oxidoreductase;

wherein said microbial organism comprising (ii) comprises five exogenous nucleic acids encoding a pyruvate:ferredoxin oxidoreductase, a phosphoenolpyruvate carboxylase, a phosphoenolpyruvate carboxykinase, a CO dehydrogenase, and an H 2 hydrogenase; or

wherein said microbial organism comprising (iii) comprises two exogenous nucleic acids encoding a CO dehydrogenase and an H 2 hydrogenase.

10 . A method for producing caprolactone, comprising culturing the non-naturally occurring microbial organism of claim 1 under conditions and for a sufficient period of time to produce caprolactone.

11 . Culture medium comprising bioderived caprolactone, wherein said bioderived caprolactone has a carbon-12, carbon-13 and carbon-14 isotope ratio that reflects an atmospheric carbon dioxide uptake source.

12 . The culture medium of claim 11 , wherein said culture medium is separated from a non-naturally occurring microbial organism having a caprolactone pathway.

13 . Bioderived caprolactone having a carbon-12, carbon-13 and carbon-14 isotope ratio that reflects an atmospheric carbon dioxide uptake source.

14 . The bioderived caprolactone of claim 13 , wherein said bioderived caprolactone has an Fm value of at least 80%, at least 85%, at least 90%, at least 95% or at least 98%.

15 . A composition comprising said bioderived caprolactone of claim 13 and a compound other than said bioderived caprolactone.

16 . The composition of claim 15 , wherein said compound other than said bioderived caprolactone is a trace amount of a cellular portion of a non-naturally occurring microbial organism having a caprolactone pathway.

17 . (canceled)

18 . A biobased polymer comprising said bioderived caprolactone of claim 13 .

19 .- 20 . (canceled)

21 . A biobased resin comprising said bioderived caprolactone of claim 13 .

22 . (canceled)

23 . A molded product obtained by molding a biobased polymer or resin of claim 18 .

24 . (canceled)

25 . A process for producing a biobased polymer or resin of claim 18 comprising chemically reacting said bioderived caprolactone with itself or another compound in a polymer producing or a resin producting reaction.