(WO2018150379) Synthesis of pheromones and related materials via olefin metathesis 机翻标题: 暂无翻译,请尝试点击翻译按钮。

源语言标题
(WO2018150379) Synthesis of pheromones and related materials via olefin metathesis
公开号/公开日
WO2018150379 WO2018150379 / 2018-08-23 2018-11-08
申请号/申请日
WOIB2018050980 / 2018-02-17
发明人
WAMPLER KEITH M BUI VU ROZZELL DAVID COELHO PEDRO FLORUTI ARTHUR ONDI LEVENTE MEHDI HASAN EROS GABOR
申请人
PROVIVI
主分类号
IPC分类号
C07C-029/00
摘要
(WO2018150379)
Methods for preparation of olefins, including 8- and 11-unsaturated monoenes and polyenes, via transition metathesis-based synthetic routes are described.Metathesis reactions in the methods are catalyzed by transition metal catalysts including tungsten-, molybdenum-, and ruthenium-based catalysts.The olefins include insect pheromones useful in a number of agricultural applications.
机翻摘要
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地址
代理人
(WO2018150379) PRESLEY, Andrew D. ([US])
代理机构
优先权号
2017US-62460661 2017US-62460667 2017US-62511903
主权利要求
(WO2018150379)
1. WHAT IS CLAIMED IS: 1. A method for synthesizing a fatty olefin derivative, the method comprising: 
 a) contacting an olefin according to Formula I R2^ (I), 
 with a metathesis reaction partner according to Formula II Γ ' (II), 
 in the presence of a metathesis catalyst under conditions sufficient to form a metathesis product according to Formula III: R y (III); and 
 b) converting the metathesis product to the fatty olefin derivative; 
 wherein: 
 R1is selected from the group consisting of hydrogen and Ci-is alkyl; 
 R2is Ci-is alkyl; 
 R3is selected from the group consisting of Ci-is alkyl and hydrogen; 
 R4is selected from the group consisting of -CFhOR43and -C(0)OR4b; 
 R4ais selected from the group consisting of -C(0)R4c, an alcohol protecting group, and hydrogen; 
 R4bis selected from the group consisting of hydrogen and Ci-8 alkyl; 
 R4cis Ci-5 alkyl; and 
 subscript y is 9 or 6. 2. The method of claim 1, wherein R4is -CFhOR43in the metathesis reaction partner of Formula II. 3. The method of claim 2, wherein R4ais -C(0)R4c
. 4. The method of claim 3, wherein the fatty olefin derivative is obtained without converting step b as metathesis product according to the formula:
5. The method of claim 2, wherein R4ais an alcohol protecting group and converting the metathesis product to the fatty olefin derivative comprises deprotecting the metathesis product to form an alkenol according to Formula IV: 
 Κ2β^ΟΗ(IV)
6. The method of claim 5, wherein converting the metathesis product to the fatty olefin derivative further comprises contacting the alkenol with an acylating agent under conditions sufficient to form an alkenol ester according to Formula V: 
 wherein R4cis selected from the group consisting of hydrogen, C1-5 alkyl, and Ci-5 haloalkyl, and 
 wherein the alkenol ester is the fatty olefin derivative. 7. The method of claim 1, wherein subscript y is 9. 8. The method of claim 7, wherein the metathesis reaction partner according to Formula II is hexadec- 1 1 -en- 1 -ol or an ester thereof. 9. The method of claim 7, wherein the metathesis reaction partner according to Formula II is a Δ1 1 -unsaturated fatty acid alkyl ester, a protected Δ1 1- unsaturated fatty alcohol, or a Δ11 -unsaturated fatty alcohol. 10. The method of claim 9, wherein the Δ1 1-unsaturated fatty acid alkyl ester, protected Δ1 1-unsaturated fatty alcohol, or Δ1 1-unsaturated fatty alcohol is derived from a natural oil. 11. The method of claim 7, wherein the olefin according to Formula I is selected from the group consisting of but-l-ene, hex-l-ene, hept- l-ene, oct-l-ene, and dec- 1- ene. 12. The method of claim 1 1, wherein the fatty olefin derivative is selected from the group consisting of (Z)- 1 1 -tetradecen- 1 -ol, (Z)-\ \ -hexadecen- 1 -ol, (Z)- 1 1 - octadecen-l-ol, and (Z)-l 1-eicosen- l-ol.
13. The method of claim 1 1, wherein the fatty olefin derivative is selected from the group consisting of (Z)- 11 -tridecenyl acetate, (Z)-\ \ -tetradecenyl acetate, (Z)- 11- hexadecenyl acetate, (Z)-l 1-hexadecenyl formate, (Z)-\ 1-hexadecenyl trifluoroacetate, (Z)- 1 1-heptadecenyl acetate, (Z)- \ 1-octadecenyl acetate, and (Z)-\ 1-eicosenyl acetate. 14. The method of claim 1 1, wherein the fatty olefin derivative is selected from the group consisting of (Z)- 1 1 -tetradecenal, (Z)-\ \ -hexadecenal, (Z)-\ \ -octadecenal, and (Z)- l l-eicosenal. 15. The method of claim 1, wherein subscript y is 6. 16. The method of claim 15, wherein the olefin is selected from the group consisting of but-l-ene, pent-l-ene, hex-l-ene, hept-l-ene, oct- l-ene, and 7-methyl-l- nonene. 17. The method of claim 16, wherein the fatty olefin derivative is selected from the group consisting of (£)-8-dodecen- l-ol, (Z)-8-dodecen- l-ol, (Z)-8-tetradecen-l-ol, (£)-14-methyl-8-hexadecen-l-ol, and (Z)-14-methyl-8-hexadecen- l-ol. 18. The method of claim 16, wherein the fatty olefin derivative is selected from the group consisting of (£)-8-undecenyl acetate, (Z)-8-undecenyl acetate, (E)-8- dodecenyl acetate, (Z)-8-dodecenyl acetate, (£)-8-tridecenyl acetate, (Z)-8-tridecenyl acetate, (£)-8-tetradecenyl acetate, (£)-8-tetradecenyl formate, (Z)-8-tetradecenyl acetate, (2)-8- tetradecenyl formate, and (Z)-8-pentadecenyl acetate. 19. A method for synthesizing a fatty polyene derivative, the method comprising: 
 a) contacting an olefin according to Formula XI 
R2^ ^/ χ Rl(XI), 
 with a metathesis reaction partner according to Formula XII y (XII), 
 in the presence of a metathesis catalyst under conditions sufficient to form a 
 metathesis product according to Formula XIII: 
 b) and optionally converting the metathesis product to the fatty olefin derivative; wherein: 
 R1and R3are independently selected from tlie group consisting of hydrogen, C i-is alky 1 , and Ci- 18 alkenyl ; 
 R2is selected from the group consisting of Ci-is alkyl and C2-18 alkenyl; 
 R4is selected from the group consisting of -CH2X, -CH2OR4a, -C(0)OR4b, and -COC(0)R4c; 
 X is halogen; 
 R4ais selected from tlie group consisting of an alcohol protecting group and hydrogen; R4bis selected from the group consisting of hydrogen and Ci-s alkyl; 
 R4cis selected from the group consisting of hydrogen, C1-5 alkyl. and C1-5 haloalkyl; subscript x is 0 or 1 ; and 
 subscript y is an integer ranging from 0 to 15. 20. The method of claim 19, further comprising converting an alcohol according to Formula XVII: 
 OH (XVII), 
 a compound according to Formula XVIII: ""- ^ ^^R6 (XVIII), 
 wherein R6is a leaving group; and 
 eliminating tlie leaving group to form an olefin according to Formula XIa: 
 (XIa). 21. The method of claim 20, wherein the olefin according to Formula XIa is (Z)-hexa- l,3-diene. 22. The method of claim 19, wherein the metathesis reaction partner is an ester according to Formula XIIc (XIIc), and wherein the fatty olefin derivative is obtained as metathesis product according to Formula XV: 
 O 
¾^ wv^cr^R4C
 without converting step (b). 23. The method of claim 19, wherein the metathesis reaction is partner is a compound according to Formula Xlld ; λ(xnd)^
 the metathesis pro Formula Xllld 
 converting the metathesis product to the fatty olefin derivative comprises contacting the halide according to Formula Xllld with a Ci-8 alkanoate under conditions sufficient to form an alkenol ester according to Formula XV: 
 wherein the alkenol ester is the fatty olefin derivative. 24. The method of claim 19, wherein R4is -CFhOR43in the metathesis reaction partner of Formula XII. 25. The method of claim 24, wherein converting the metathesis product to the fatty olefin derivative comprises deprotecting the metathesis product to form an alkenol according to Formula XIV:
26. The method of claim 25, wherein converting the metathesis product to the fatty olefin derivative further comprises contacting the alkenol with an acylating agent under conditions sufficient to form an alkenol ester according to Formula XV: (XV), wherein R4cis selected from the group consisting of hydrogen, C1-5 alkyl, and Ci-5 haloalkyl, and 
 wherein the alkenol ester is the fatty olefin derivative. 27. The method of claim 19, wherein R4is -C(0)OR4bin the metathesis reaction partner according to Formula XII. 28. The method of claim 27, wherein converting the metathesis product to the fatty olefin derivative comprises contacting the metathesis product with a reducing agent under conditions sufficie to Formula XIV: (XIV). 29. The method of claim 28, wherein converting the metathesis product to the fatty olefin derivative further comprises contacting the alkenol with an acylating agent under conditions sufficient to form an alkenol ester according to Formula XV: 
 wherein R4cis selected from the group consisting of hydrogen, C1-5 alkyl, and Ci-5 haloalkyl, and 
 wherein the alkenol ester is the fatty olefin derivative. 30. The method of claim 19, wherein the olefin according to Formula XI is selected from the group consisting of (£)-pent-l,3-diene, (Z)-pent-l,3-diene, (E)-hepta-l,3- diene, (Z)-hepta-l,3-diene, (£)-octa-l,3-diene, and (Z)-octa-l,3-diene. 31. The method of claim 19, wherein the fatty polyene derivative is selected from the group consisting of (E,E)-8, 10-dodecadien- 1 -ol, (i?,Z)-8, 10-dodecadien- 1 - ol, (Z,£)-8,l 0-dodecadien- l-ol, (Z,Z)-8, 10-dodecadien-l-ol, and (E,E)-8,10-tetradecadien-l- ol. 32. The method of claim 19, wherein the fatty polyene derivative is selected from the group consisting of (i?,£)-8,10-dodecadienyl acetate, (E,Z)-8,10- dodecadienyl acetate, (Z,£)-8,10-dodecadienyl acetate, (Z,Z)-8,10-dodecadienyl acetate, (i?,£)-8, 10-tetradecadienyl acetate, (i?,£)-8, 10-pentadecadienyl acetate, (E,Z)-8,10- pentadecadienyl acetate, (Z,£)-8, 10-pentadecadienyl acetate, and (Z,Z)-8, 10-pentadecadienyl acetate. 33. The method of claim 19, wherein the fatty polyene derivative is selected from the group consisting of (i?,£)-8, 10-dodecadienal, (i?,Z)-8, 10-dodecadienal, (Z,£)-8, 10-dodecadienal, (E,E)-8, 10-tetradecadienal, and (i?,Z)-8, 10-tetradecadienal. 34. A method for synthesizing a fatty olefin derivative, the method comprising: 
 a) contacting an olefin according to Formula XXI " ^¾l"R2(XXI) 
 with a po to Formula XXII (XXII) in the presence of a metathesis catalyst under conditions sufficient to form a m a XXIII (XXIII); and 
 b) optionally converting the metathesis product to the fatty olefin derivative; 
 wherein: 
 R1and R3are independently selected from the group consisting of hydrogen, Ci-is alkyl, and C2-18 alkenyl; 
 R2is selected from the group consisting of Ci-is alkyl and C2-18 alkenyl; 
 R4is selected from the group consisting of -COC(0)R4a, -CH2OR4b, -C(0)OR4c, and 
 R4ais selected from the group consisting of hydrogen, C1-5 alkyl, and C1-5 haloalkyl; R4bis an alcohol protecting group; 
 R4cis selected from the group consisting of hydrogen and Ci-8 alkyl; 
 X is halogen; 
 subscript m is 0 or 1; and 
 subscript n is an integer ranging from 0 to 15.
35. The method of claim 34, wherein the polyene reaction partner is an ester according to Formula XXIIa 
 wherein the fatty olefin derivative is obtained as a metathesis product according to Formula XXIIIa (XXIIIa) without converting step (b).
36. The method of claim 35, wherein the ester according to Formula XXIIa is obtained by a process comprising: 
 converting an in rnal olefin according to Formula XXIIa-i (XXIIa-i) to the ester according to Formula XXIIa, 
 wherein R5is a leaving group.
37. The method of claim 36, wherein the leaving group is selected from the group consisting of a sulfonate and a halide.
38. The method of claim 36, wherein the internal olefin according to Formula XXIIa-i is obtained by a process comprising 
 contacting a compound according to Formula XXIIa-iii (XXIIa-iii) 
 with a reaction partner according to formula XXIIa-ii (XXIIa-ii) in the presence of an intermediate catalyst under conditions sufficient to form the internal olefin according Formula XXIIa-i; 
 wherein R6and R7are independently selected from the group consisting of hydrogen, Ci-18 alkyl, and C2-18 alkenyl. 39. The method of claim 36, wherein R5is mesylate or tosylate. 40. The method of claim 34, wherein the olefin is selected from the group consisting of but-l-ene, pent-l-ene, hex-l-ene, hept-l-ene, oct-l-ene, and 7-methyl-l- nonene. 41. The method of claim 34, wherein the fatty olefin derivative is selected from the group consisting of (7E,9Z) dodeca-7,9-dien-l-yl acetate and (8E, 10£)-dodeca- 8,10-dien-l-ol. 42. A method for synthesizing a fatty olefin derivative, the method comprising: 
 a) contacting an olefin according to Formula XXXI R22^ ^ -Rl(XXXI), 
 with a metathes er according to Formula XXXII (XXXII), 
 in the presence of a metathesis catalyst under conditions sufficient to form a metathesis product according to Formula XXXIII: 
 o2jjJ=rR4(XXXIII); and 
 b) optionally converting the metathesis product to the fatty olefin derivative; 
 wherein: 
 R1and R3are independently selected from the group consisting of hydrogen and C1-18 alkyl; 
 R2is selected from the group consisting of C1-18 alkyl and C2-18 alkenyl; 
 R4is selected from the group consisting of -CH2OR4a, -C(0)OR4b, -CH2OC(0)R4c, and halogen; 
 R4ais selected from the group consisting of hydrogen and an alcohol protecting group; R4bis selected from the group consisting of hydrogen and Ci-8 alkyl; R4cis selected from the group consisting of hydrogen, Ci-8 alkyl, and Ci-8 haloalkyl; and 
 subscript x is an integer ranging from 3 to 15. 43. The method of claim 42, further comprising: 
 i) dehydrating a diol according to Formula XXXVII: 
 HO. 
 OH 
 x (XXXVII) 
 to form the an alkenol according to Formula XXXIId: 'x(XXXIId). 44. The method of claim 43, further comprising protecting the alkenol to form the metathesis reaction partner according to Formula XXXIIa x (XXXIIa), 
 wherein R4ais an alcohol protecting group. 45. The method of claim 43, further comprising acylating the alkenol to form the metathesis reaction partner according to Formula XXXIIc: (XXXIIc). 46. The method of claim 42, further comprising: 
 i) converting a diol according to Formula XXXVII: 
 HO. ^\ 
\^ "/OH 
 x (XXXVII) 
 to an alcohol according to Formula XXXVIII: (XXXVIII), 
 wherein R5is a leaving group; 
 ii) acylating the alcohol to form an ester according to Formula XXXIXb (XXXIXc); and iii) eliminating leaving group R5to form the metathesis reaction partner according to Formula lie: (XXXIIc). 47. The method of claim 42, wherein R4ain the metathesis reaction product is an alcohol protecting group, and wherein converting the metathesis product to the fatty olefin derivative comprises deprotecting the metathesis product to form an alkenol according to Formula XXXIV: ^^ X^oh(XXXIV). 48. The method of claim 47, wherein converting the metathesis product to the fatty olefin derivative comprises contacting the alkenol according to Formula XXXIV with an acylating agent under conditions sufficient to form an alkenol ester according to Formula XXXV: 
 wherein R4cis selected from the group consisting of hydrogen, C1-5 alkyl, and Ci-5 haloalkyl, and 
 wherein the alkenol ester is the fatty olefin derivative. 49. The method of claim 42, wherein R4is halogen and converting the metathesis product to the fatty olefin derivative comprises contacting the metathesis product with a carboxylate salt under conditions sufficient to form an alkenol ester according to Formula XXXV: 
 wherein R4cis selected from the group consisting of hydrogen, C1-5 alkyl, and Ci-5 haloalkyl, and 
 wherein the alkenol ester is the fatty olefin derivative.
50. The method of claim 47, wherein converting the metathesis product to the fatty olefin derivative comprises contacting the alkenol according to Formula XXXIV with an oxidizing agent under conditions sufficient to form an alkenal according to Formula XXXVI: (XXXVI), 
 wherein the alkenal is the fatty olefin derivative. 51. The method of claim 42, wherein the olefin is selected from the group consisting of but-l-ene, pent-l-ene, hex-l-ene, hept-l-ene, oct-l-ene, 7-methyl-l-nonene, and fr «5-l,3-pentadiene. 52. The method of claim 51, wherein the fatty olefin derivative is selected from the group consisting of (£)-dec-5-en-l-ol and (8ii,10£)-dodeca-8,10-dien-l-ol. 53. The method of claim 51, wherein the fatty olefin derivative is selected from the group consisting of (£)-dec-5-en-l-yl acetate, (Z)-dodec-7-en-l-yl acetate; (Z)- dodec-8-en-l-yl acetate; (Z)-dodec-9-en-l-yl acetate; (Z)-tetradec-9-en-l-yl acetate; (Z)- tetradec-11-en-l-yl acetate; (Z)-hexadec- 11-e n-l-yl acetate; and (7E,9Z) dodeca-7,9-dien-l- yl acetate. 54. The method of claim 51, wherein the fatty olefin derivative is selected from the group consisting of (Z)-hexadec-9-enal, (Z)-hexadec-l 1-enal, and (Z)-octadec-13- enal. 55. The method of claim 1, wherein the metathesis product comprises a Z olefin. 56. The method of claim 55, wherein at least about 80% of the olefin is a Z olefin. 57. The method of claim 55, wherein at least about 90% of the olefin is a Z olefin. 58. The method of claim 1, wherein the metathesis catalyst is a Z-selective molybdenum catalyst, a Z-selective tungsten catalyst, or a Z-selective ruthenium catalyst.
59. The method of claim 58, wherein the metathesis catalyst has a structure according to Formula XLII: 
 wherein: 
 M is Mo or W; 
 R6ais selected from the group consisting of aryl, heteroaryl, alkyl, heteroalkyl, cycloalkyl, and heterocycloalkyl, each of which is optionally substituted; R7aand R8aare independently selected from the group consisting of hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted heteroalkyl, optionally substituted heteroalkenyl, optionally substituted aryl, and optionally substituted heteroaryl; 
 R10ais selected from the group consisting of alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, and silyloxy, each of which is optionally substituted; and R9ais Rl la-X-, wherein 
 X is O or S and Rl lais optionally substituted aryl; or 
 X is O and Rl lais SiR12aR13aR14aor CR15aR16aR17a, wherein R12a, R13a, R14a, R15a, R16a, and R17aare independently selected from the group consisting of optionally substituted alkyl and optionally substituted phenyl; or 
 R9aand R10aare linked together and are bonded to M via oxygen. 60. The method of claim 59, wherein: 
 R10ais selected from the group consisting of alkyl, alkoxy, heteroalkyl, aryl, aryloxy, and heteroaryl, each of which is optionally substituted; and 
 X is O or S and Rl lais optionally substituted aryl; or 
 X is O and Rl lais CR15aR16aR17a
. 61. The method of claim 59, wherein 
 R6ais selected from the group consisting of 2,6-dimethylphenyl; 2,6- diisopropylphenyl; 2,6-dichlorophenyl; and adamant- 1-yl; 
 R7ais selected from the group consisting of -C(CH3)2CeH5 and -C(CH3)3 ; 
 R8ais H; R10ais selected from the group consisting of pyrrol-l-yl; 2,5-dimethyl-pyrrol-l-yl; triphenylsilyloxy; triisopropylsilyloxy; 2-phenyl-l,l,l,3,3,3-hexafluoro-prop- 2-yloxy; 2-methyl-l,l, l,3,3,3-hexafluoro-prop-2-yloxy; 9-phenyl-fluorene-9- yloxy; 2,6-diphenyl-phenoxy; and i-butyloxy; and 
 R9ais Rl la-X-, wherein 
 X = O and 
 Rl lais phenyl which bears two substituents in the ortho positions with respect to O, or which bears at least three substituents, from which two substituents are in the ortho positions with respect to O and one substituent is in the para position with respect to O; or 
 Rl lais selected from the group consisting of optionally substituted 8-(naphthalene-l-yl)-naphthalene-l-yl; optionally substituted 8-phenylnaphthalene-l-yl; optionally substituted quinoline-8-yl; triphenylsilyl; triisopropylsilyl; triphenylmethyl; tri(4-methylphenyl)methyl; 9-phenyl-fluorene-9-yl; 2-phenyl-l, l, l,3,3,3-hexafluoroprop-2-yl; 2-methyl- l, l,l,3,3,3-hexafluoro-prop-2-yl; and t-butyl. 62. The method of claim 61, wherein: 
 R10ais selected from the group consisting of pyrrol-l-yl; 2,5-dimethyl-pyrrol-l-yl; and 
 Rl lais phenyl which bears two substituents in the ortho positions with respect to O, or which bears at least three substituents, from which two substituents are in the ortho positions with respect to O and one substituent is in the para position with respect to O; or 
 Rl lais selected from the group consisting of optionally substituted 8-(naphthalene-l-yl)-naphthalene-l-yl and optionally substituted 8-phenylnaphthalene-l-yl. 63. The method of claim 59, wherein the metathesis catalyst has a structure according to Formula XLIIa: 
 Rl ac T T 
 R8aR7b(XLIIa) R6ais aryl, heteroaryl, alkyl, or cycloalkyl, each of which is optionally substituted; R10ais pyrrolyl, imidazolyl, indolyl, pyrazolyl, azaindolyl, or indazolyl, each of which is optionally substituted; 
 Rl lais optionally substituted aryl; 
 R8ais a hydrogen atom, alkyl, or alkoxy; 
 R713is a hydrogen atom, -0-(Ci-6 alkyl), -CH2-0-( Ci-6 alkyl), heteroalkoxy, or -N(Ci-6 alkyl)2; 
 R7cand R7dare independently a hydrogen atom, Ci-6 alkyl, Ci-6 alkoxy, a halogen atom, -NO2, an amide, or a sulfonamide. 64. The method of claim 63, wherein: 
 R10ais pyrrolyl, imidazolyl, pyrazolyl, azaindolyl, or indazolyl, each of which is optionally substituted; and 
 R8ais a hydrogen atom. 65. The method of claim 63, wherein R6ais phenyl, 2,6-dichlorophenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2-trifluoromethylphenyl, pentafluorophenyl, tert- butyl, or 1-adamantyl. 66. The method of R6ais 

67. The method of claim 63, wherein R7bis methoxy, R7cis hydrogen, and R7dis hydrogen.
68. The method of claim 58, wherein the metathesis catalyst is selected from the group consisting of 

69. The method of claim 58, wherein the metathesis catalyst has a structure 
 (XLIV), 
 wherein: 
 Q is selected from hydrocarbylene, substituted hydrocarbylene, heteroatom- containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene, wherein two or more substituents on adjacent atoms within Q may also be linked to form an additional cyclic structure; 
 Q* forms a carbon-ruthenium bond with the carbon from the R41group; 
 R40and R41are independently selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; 
 R42is selected from halide, nitrate, alkyl, aryl, alkoxy, alkylcarboxylate, aryloxy, alkoxy carbonyl, aryloxy carbonyl, arylcarboxylate, acyl, acyloxy, alkylsulfonato, arylsulfonato, alkylsulfanyl, arylsulfanyl, alkylsulfinyl, and arylsulfinyl; 
 R43is selected from hydrogen, alkyl, and aryl, wherein alkyl and aryl are optionally substituted with one or more functional groups selected from the group consisting of alkoxy, aryloxy, halogen, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, trifluoroamide, sulfide, disulfide, carbamate, silane, siloxane, phosphine, phosphate, or borate; methyl, isopropyl, sec-butyl, t-butyl, neopentyl, benzyl, phenyl and trimethylsilyl; and 
 R44, R45, R46, and R47are independently selected from the group consisting of 
 hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, halogen-substituted amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, or borate, wherein any combination of R44, R45, R46, and R47is optionally linked to form one or more cyclic groups. 70. The method of claim 1, wherein the metathesis catalyst is present in an amount less than 0.01 mol% with respect to the olefin or to the metathesis reaction partner. 71. The method of claim 1, wherein the metathesis product comprises an E olefin.
72. Tlie method of claim 71, wherein greater than about 85% of the olefin is an E olefin. 73. The method of claim 71 , wherein at least about 90% of the olefin is an E olefin. 74. Tlie method of claim 71, wherein the metathesis catalyst is an E- selective ruthenium catalyst.
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