CN111995488B - Preparation method of fused ring compound - Google Patents

Preparation method of fused ring compound Download PDF

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CN111995488B
CN111995488B CN201910445843.5A CN201910445843A CN111995488B CN 111995488 B CN111995488 B CN 111995488B CN 201910445843 A CN201910445843 A CN 201910445843A CN 111995488 B CN111995488 B CN 111995488B
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ring
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CN111995488A (en
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林国强
冯陈国
魏东
李梦尧
朱彬彬
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Shanghai Institute of Organic Chemistry of CAS
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Abstract

The invention discloses a preparation method of a fused ring compound III. The preparation method comprises the following steps: the compound III can be obtained by reacting the compound I and the compound II in a solvent in the presence of palladium acetate, alkali and a ligand as shown below. The preparation method has good compatibility to substrates, can obtain a plurality of condensed ring aromatic compounds in a short time by convergent synthesis, and particularly shows extremely excellent regioselectivity for condensed ring aromatic hydrocarbons containing heteroatoms.

Description

Preparation method of fused ring compound
Technical Field
The present invention relates to a method for producing a fused ring compound.
Background
The polycyclic aromatic hydrocarbon skeleton is widely present in natural product, active drug and functional material molecules, and the molecules are more applied to the research of medicine, agriculture, grass science, pharmacy, optics, electricity and materials science. Among them, substituted phenanthrene ring compounds are attracting attention from scientists due to their unique optical properties.
The currently known methods for synthesizing substituted phenanthrene ring compounds are: 1. synthesizing a phenanthrene ring by a coupling or cyclization strategy from substituted biphenyl; 2.1, 2-disubstituted benzene (stilbene) is reacted with unsaturated compounds through a free radical or ionic mechanism to prepare phenanthrene rings. Although the two strategies can successfully synthesize various substituted phenanthrene compounds, the preparation of raw materials needs multi-step reaction to obtain the substituted phenanthrene compounds, and some raw materials with relatively complex structures need to be obtained at a great cost, and meanwhile, the applicability of the substrate is limited. In the known synthetic methods, the compatibility of the fused ring aromatic compounds similar to the phenanthrene ring framework is poor, and the fused ring compounds with more different frameworks are rarely reported.
Therefore, the development of a simple and multi-substrate applicable fused ring compound preparation method becomes the focus of the current research.
Disclosure of Invention
The invention aims to solve the problems that in the prior art, the preparation route of the fused ring compound has complex steps, raw materials are not easy to obtain, the substrate applicability is limited, the compatibility of the synthesis method of the phenanthrene ring framework to the fused ring compound is poor, and the like, and provides the preparation method of the fused ring compound. The preparation method of the invention uses common commercial brominated aromatic hydrocarbon and easily synthesized 1, 1-diaryl substituted olefin to efficiently synthesize the condensed ring compound, has better compatibility to substrates, can obtain a plurality of condensed ring aromatic hydrocarbon compounds in a short time by convergent synthesis, and particularly shows extremely excellent regioselectivity for the condensed ring aromatic hydrocarbon containing heteroatom.
The invention provides a preparation method of a fused ring compound III, which comprises the following steps: in a solvent, in the presence of palladium acetate, alkali and a ligand, carrying out the reaction shown as the following on a compound I and a compound II to obtain a compound III;
the ligand is
Figure BDA0002073604040000021
HPCy 3 BF 4 、
Figure BDA0002073604040000022
R is H, 4-OMe or 4-CF 3 ；
Figure BDA0002073604040000023
X is bromo, chloro or trifluoromethanesulfonyl;
Figure BDA0002073604040000024
and
Figure BDA0002073604040000025
independently a single or double bond;
Figure BDA0002073604040000026
represents R 2 And R 1 The double bond between them is in E and/or Z configuration;
ring A and ring B are independently C 6 -C 30 Aromatic ring, by one or more R 1-1 Substituted C 6 -C 30 An aromatic ring, a 5-to 14-membered heteroaromatic ring having one or more heteroatoms selected from N, O and S and 1-3 heteroatoms, or substituted with one or more R 1-2 Substituted "5-14 membered heteroaromatic ring with 1-3 heteroatoms selected from one or more of N, O and S; when there are more than one R 1-1 When substituted, said R 1-1 The same or different; when there are more than one R 1-2 When substituted, said R 1-2 The same or different;
R 1-1 and R 1-2 Independently selected from the following substituents: halogen, C 1 -C 10 Alkyl radical, C 1 -C 10 Alkoxy, D, trifluoromethanesulfonyl, halo C 1 -C 4 Alkyl radical, C 1 -C 10 An alkyl-substituted mercapto group,
Figure BDA0002073604040000027
"5-6 membered heteroaryl group containing 1 to 3 hetero atoms selected from N, O and S, one or more hetero atoms 6 -C 14 Aryl radical, C 6 -C 10 Aryl substituted C 6 -C 14 Aryl and
Figure BDA0002073604040000031
wherein R' is H, C 1 -C 4 Alkyl or C 1 -C 4 An alkoxy group; r a 、R b And R c Independently is C 1 -C 4 An alkyl group;
R 3 h, D or trifluoromethanesulfonyl;
R 1 is C 6 -C 14 Aryl radicals, substituted by one or more R 2-1 Substituted C 6 -C 14 Aryl, 5-6 membered heteroaryl with one or more heteroatoms selected from N, O and S, 1-3 heteroatoms, and one or more R 2-2 Substituted 'one or more hetero atoms selected from N, O and S, 5-6 membered heteroaryl with 1-3 hetero atoms', C 1 -C 10 Alkyl or
Figure BDA0002073604040000032
Wherein R' is C 1 -C 4 An alkyl group; when there are more than one R 2-1 When substituted, said R 2-1 The same or different; when there are more than one R 2-2 When substituted, said R 2-2 The same or different;
R 2-1 and R 2-2 Independently selected from the following substituents: halogen, C 1 -C 10 Alkyl and C 1 -C 10 An alkoxy group;
R 2 is hydrogen or C 1 -C 4 An alkyl group.
When said compound II, except R 3 In addition, X is not R in the ortho-position X Substituent (e.g. of
Figure BDA0002073604040000033
Wherein R is 6 Is C 1 -C 4 Alkyl), or, the ortho position of X is annulated to the meta position of X (e.g. by cyclization)
Figure BDA0002073604040000034
R 7 And R 8 Carbon attached thereto forms a ring), R X In the case of H, D or trifluoromethanesulfonyl, the reactive sites in compound II are the carbon attached to X and the carbon attached to R 3 Attached carbon, said compound III
Figure BDA0002073604040000035
Is a single product.
When the compound II is
Figure BDA0002073604040000041
R 4 In the case of H, D or trifluoromethanesulfonyl, the reactive sites in compound II are "carbon attached to X and" carbon attached to R 3 Attached carbon, and/or, carbon attached to X and carbon attached to R 4 Attached carbon ", said compound III being
Figure BDA0002073604040000042
And/or
Figure BDA0002073604040000043
Wherein the content of the first and second substances,
Figure BDA0002073604040000044
and
Figure BDA0002073604040000045
each independently represents a single bond or a double bond, and the two are not a single bond or a double bond at the same time; ring C is C 6 -C 30 Aromatic ring, by one or more R 3-1 Substituted C 6 -C 30 An aromatic ring, a 5-to 14-membered heteroaromatic ring having one or more heteroatoms selected from N, O and S and 1-3 heteroatoms, or substituted with one or more R 3-2 The substituted heteroatom is selected from one or more of N, O and S, 5-14 membered heteroaromatic ring with 1-3 heteroatoms”；
R 3-1 And R 3-2 Independently selected from the following substituents: halogen, C 1 -C 10 Alkyl radical, C 1 -C 10 Alkoxy, D, trifluoromethanesulfonyl, halo C 1 -C 4 Alkyl radical, C 1 -C 10 An alkyl-substituted mercapto group,
Figure BDA0002073604040000046
"5-6 membered heteroaryl group containing one or more heteroatoms selected from N, O and S and having 1-3 heteroatoms", and C 6 -C 14 Aryl radical, C 6 -C 10 Aryl substituted C 6 -C 14 Aryl and
Figure BDA0002073604040000047
wherein R' "is H, C 1 -C 4 Alkyl or C 1 -C 4 An alkoxy group; r d 、R e And R f Independently is C 1 -C 4 An alkyl group;
when there are more than one R 3-1 When substituted, said R 3-1 The same or different; when there are more than one R 3-2 When substituted, said R 3-2 The same or different.
Said ring A is preferably C 6 -C 30 Aromatic ring, by one or more R 1-1 Substituted C 6 -C 30 An aromatic ring, or a 5-14 membered heteroaromatic ring having 1 heteroatom, "heteroatom N, O or S".
In ring A, the R is 1-1 Preferably halogen, C 1 -C 10 Alkyl radical, C 1 -C 10 Alkoxy or halo C1-C4 alkyl.
Said R 1 Preferably C 6 -C 14 Aryl radicals, substituted by one or more R 2-1 Substituted C 6 -C 14 Aryl radical, by one or more R 2 -2 Substituted 'one or more hetero atoms selected from N, O and S, 5-6 membered heteroaryl with 1-3 hetero atoms', C 1 -C 10 Alkyl or
Figure BDA0002073604040000051
Wherein R' is C 1 -C 4 An alkyl group. Said R 2-1 Preferably halogen or C 1 -C 10 An alkyl group. Said R 2-2 Preferably C 1 -C 10 An alkoxy group.
The ring B is preferably C 6 -C 30 Aromatic ring, by one or more R 1-1 Substituted C 6 -C 30 An aromatic ring or "a 5-to 14-membered heteroaromatic ring having 1 to 3 heteroatoms from which the heteroatoms are selected from one or more of N, O and S".
Said X is preferably bromine.
Said ring C is preferably C 6 -C 30 An aromatic ring or "a 5-to 14-membered heteroaromatic ring having 1 to 3 heteroatoms from which the heteroatoms are selected from one or more of N, O and S".
Said R 3 Preferably H or D.
Said R 4 Preferably H or D.
In a preferred group of embodiments, the ring A is C 6 -C 30 Aromatic ring, by one or more R 1-1 Substituted C 6 -C 30 An aromatic ring, or a 5-14 membered heteroaromatic ring having "N, O or S as heteroatoms and 1"; in ring A, the R is 1-1 Is halogen, C 1 -C 10 Alkyl radical, C 1 -C 10 Alkoxy or halo C1-C4 alkyl; said R 1 Is C 6 -C 14 Aryl radicals, substituted by one or more R 2-1 Substituted C 6 -C 14 Aryl radicals, substituted by one or more R 2-2 Substituted 'one or more hetero atoms selected from N, O and S, 5-6 membered heteroaryl with 1-3 hetero atoms', C 1 -C 10 Alkyl or
Figure BDA0002073604040000052
Wherein R' is C 1 -C 4 An alkyl group; in ring A, the R is 2-1 Is halogen or C 1 -C 10 An alkyl group; said R 2-2 Is C 1 -C 10 An alkoxy group; the ring B is C 6 -C 30 Aromatic ring, by one or more R 1-1 Substituted C 6 -C 30 Aromatic ring or "5-14 membered heteroaromatic ring with 1-3 heteroatoms selected from one or more of N, O and S", and X is bromine.
In a preferred group of embodiments, the ring A is C 6 -C 30 Aromatic ring, by one or more R 1-1 Substituted C 6 -C 30 An aromatic ring, or a 5-14 membered heteroaromatic ring having "N, O or S as heteroatoms and 1"; in ring A, the R is 1-1 Is halogen, C 1 -C 10 Alkyl radical, C 1 -C 10 Alkoxy or halo C1-C4 alkyl; said R 1 Is C 6 -C 14 Aryl radicals, substituted by one or more R 2-1 Substituted C 6 -C 14 Aryl radicals, substituted by one or more R 2-2 Substituted 'one or more hetero atoms selected from N, O and S, 5-6 membered heteroaryl with 1-3 hetero atoms', C 1 -C 10 Alkyl or
Figure BDA0002073604040000061
Wherein R' is C 1 -C 4 An alkyl group; in ring A, the R is 2-1 Is halogen or C 1 -C 10 An alkyl group; said R 2-2 Is C 1 -C 10 An alkoxy group; the ring C is C 6 -C 30 An aromatic ring or a "5-14 membered heteroaromatic ring with 1-3 heteroatoms selected from one or more of N, O and S; x is bromine; said R 4 Preferably H or D.
In a preferred group of embodiments, ring A is C 6 -C 30 Aromatic ring, by one or more R 1-1 Substituted C 6 -C 30 An aromatic ring, or a 5-14 membered heteroaromatic ring having 1 heteroatom atom "N, O or S", R 1 Is C 6 -C 14 Aryl, or C substituted by one or more halogens 6 -C 14 Aryl radical, C 1 -C 10 Alkyl or
Figure BDA0002073604040000062
R 2 Is hydrogen; ring B is C 6 -C 30 Aromatic rings or substituted by one or more R 1-1 Substituted C 6 -C 30 Aromatic ring, R 1-1 Is D, halogen, C 1 -C 4 Alkyl radical, C 1 -C 10 Alkoxy or halo C1-C4 alkyl, R 3 Is H or D, and X is bromine.
When said ring A is C 6 -C 30 When it is an aromatic ring, said C 6 -C 30 The aromatic ring is preferably C 6 -C 14 An aromatic ring. Said C 6 -C 14 The aromatic ring is preferably a benzene ring, a naphthalene ring, an anthracene ring or a phenanthrene ring. The naphthalene ring is preferably
Figure BDA0002073604040000063
When said ring A is substituted by one or more R 1-1 Substituted C 6 -C 30 When it is an aromatic ring, said C 6 -C 30 The aromatic ring is preferably C 6 -C 14 An aromatic ring. Said C 6 -C 14 The aromatic ring is preferably a benzene ring, a naphthalene ring, an anthracene ring or a phenanthrene ring. The naphthalene ring is preferably
Figure BDA0002073604040000064
When the ring a is a "5-to 14-membered heteroaromatic ring having 1 to 3 heteroatoms selected from one or more of N, O and S", the "heteroatom selected from one or more of N, O and S", the 5-to 14-membered heteroaromatic ring having 1 to 3 heteroatoms "is preferably a" 5-to 6-membered heteroaromatic ring having 1 to 3 heteroatoms selected from one or more of N, O and S ", and more preferably a" 5-to 6-membered heteroaromatic ring having N, O or S, and 1 heteroatom ", and still more preferably a pyridine ring. The pyridine ring is preferably
Figure BDA0002073604040000071
When said ring A is substituted by one or more R 1-2 The substituted heteroatom is selected from one or more of N, O and S, and 5-14 member heteroatom with 1-3 heteroatomsIn the case of the aromatic ring, the "hetero atom (S) is (are) selected from one or more of N, O and S, and the 5-to 14-membered heteroaromatic ring having 1 to 3 hetero atoms" is preferably "the hetero atom (S) is (are) selected from one or more of N, O and S, and the 5-to 6-membered heteroaromatic ring having 1 to 3 hetero atoms", and more preferably "the 5-to 6-membered heteroaromatic ring having N, O or S hetero atoms and 1 hetero atom".
When the ring B is C 6 -C 30 When it is an aromatic ring, said C 6 -C 30 The aromatic ring is preferably C 6 -C 14 An aromatic ring. Said C 6 -C 14 The aromatic ring is preferably a benzene ring, a naphthalene ring (for example,
Figure BDA0002073604040000072
) An anthracene ring or a phenanthrene ring (e.g.,
Figure BDA0002073604040000073
)。
when said ring B is substituted by one or more R 1-1 Substituted C 6 -C 30 When it is an aromatic ring, said C 6 -C 30 The aromatic ring is preferably C 6 -C 14 An aromatic ring. Said C 6 -C 14 The aromatic ring is preferably a benzene ring, a naphthalene ring, an anthracene ring or a phenanthrene ring.
When the ring B is a "5-to 14-membered heteroaromatic ring having 1 to 3 heteroatoms selected from one or more of N, O and S", the "heteroatom is one or more of N, O and S", and the "5-to 14-membered heteroaromatic ring having 1 to 3 heteroatoms" is preferably a "heteroatom selected from one or more of N, O and S, a 5-to 6-membered heteroaromatic ring having 1 to 3 heteroatoms" or a "heteroatom selected from one or more of N, O and S, and an 8-to 10-membered heteroaromatic ring having 1 to 3 heteroatoms". The "5-6 membered heteroaromatic ring having 1 to 3 hetero atoms and being selected from one or more of N, O and S" is preferably "5-6 membered heteroaromatic ring having N, O hetero atoms or S hetero atoms and 1 hetero atom", and is more preferably a thiophene ring (for example,
Figure BDA0002073604040000081
) Or a pyridine ring (for example,
Figure BDA0002073604040000082
). The "hetero atom is one or more selected from N, O and S, and the 8-to 10-membered heteroaromatic ring having 1 to 3 hetero atoms" is preferably "an 8-to 10-membered heteroaromatic ring having N, O or S hetero atoms and 1 hetero atom", "an 8-to 10-membered heteroaromatic ring having N, O or S hetero atoms and 2 hetero atoms" or "an 8-to 10-membered heteroaromatic ring having N, O and S hetero atoms and 2 hetero atoms". The "8-to 10-membered heteroaromatic ring having N, O or S as a heteroatom and 1 as a heteroatom" is preferably a quinoline ring (for example,
Figure BDA0002073604040000083
Figure BDA0002073604040000084
) An isoquinoline ring (e.g.,
Figure BDA0002073604040000085
) A benzofuran ring (e.g.,
Figure BDA0002073604040000086
) Or a benzothiophene ring (for example,
Figure BDA0002073604040000087
). The "8-to 10-membered heteroaromatic ring having N, O or S as a heteroatom and 2 as a heteroatom" is preferably a quinoxaline ring (for example,
Figure BDA0002073604040000088
). The "8-to 10-membered heteroaromatic ring containing N, O and S as two hetero atoms and 2 hetero atoms" is preferably a benzothiazole ring
Figure BDA0002073604040000089
When said ring B is substituted by one or more R 1-2 When the substituted heteroatom is one or more selected from N, O and S, and the heteroatom number is 1-3, the heteroatom is selected from 5-14 membered heteroaromatic ringN, O and S, a 5-to 14-membered heteroaromatic ring having 1 to 3 heteroatoms "is preferably" one or more heteroatoms selected from N, O and S, a 5-to 6-membered heteroaromatic ring having 1 to 3 heteroatoms "or" one or more heteroatoms selected from N, O and S, an 8-to 10-membered heteroaromatic ring having 1 to 3 heteroatoms ". The "5-6 membered heteroaromatic ring having 1 to 3 hetero atoms and one or more hetero atoms selected from N, O and S" is preferably "5-6 membered heteroaromatic ring having 1 hetero atom and N, O or S". The "hetero atom is one or more selected from N, O and S, and the 8-to 10-membered heteroaromatic ring having 1 to 3 hetero atoms" is preferably "an 8-to 10-membered heteroaromatic ring having N, O or S hetero atoms and 1 hetero atom", "an 8-to 10-membered heteroaromatic ring having N, O or S hetero atoms and 2 hetero atoms" or "an 8-to 10-membered heteroaromatic ring having N, O and S hetero atoms and 2 hetero atoms". The "8-to 10-membered heteroaromatic ring having N, O or S as a heteroatom and 1 as a heteroatom" is described.
When said R is 1-1 And R 1-2 Independently halogen, the halogen is preferably fluorine, chlorine, bromine or iodine.
When said R is 1-1 And R 1-2 Independently is C 1 -C 10 When alkyl, said C 1 -C 10 The alkyl group is preferably C 1 -C 4 Alkyl groups, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl.
When said R is 1-1 And R 1-2 Independently is C 1 -C 10 At alkoxy, said C 1 -C 10 Alkoxy is preferably C 1 -C 4 Alkoxy, for example methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy.
When said R is 1-1 And R 1-2 Independently is halo C 1 -C 4 When alkyl, said C 1 -C 4 Alkyl is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl; the halo is preferably substituted by fluoro, chloro, bromo or iodo. Said halo C 1 -C 4 Alkyl is preferably halo C 1 -C 2 Alkyl, more preferably fluoro C 1 -C 2 Alkyl, most preferably trifluoromethyl.
When said R is 1-1 And R 1-2 Independently is C 1 -C 10 When the mercapto group is substituted by an alkyl group, said C 1 -C 10 The alkyl group is preferably C 1 -C 4 Alkyl groups, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl.
When said R is a 、R b And R c Independently is C 1 -C 4 When alkyl, said C 1 -C 4 The alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a tert-butyl group.
When said R' is C 1 -C 4 When alkyl, said C 1 -C 4 The alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a tert-butyl group.
When said R' is C 1 -C 4 At alkoxy, said C 1 -C 4 The alkoxy group is preferably methoxy, ethoxy, n-oxopropyl, i-oxopropyl, n-butoxy, i-butoxy or tert-butoxy
When said R is 1-1 And R 1-2 When the "5-6 membered heteroaryl group having 1 to 3 hetero atoms and one or more hetero atoms selected from N, O and S" are independently used, the "5-6 membered heteroaryl group having 1 to 3 hetero atoms and one or more hetero atoms selected from N, O and S" is preferably used, and the "5-6 membered heteroaryl group having 1 hetero atoms and one or more hetero atoms selected from N, O and S" is more preferably used, and the "5-6 membered heteroaryl group having 1 hetero atom and one or more hetero atoms selected from the group consisting of pyridinyl (for example,
Figure BDA0002073604040000101
)。
when said R is 1-1 And R 1-2 Independently is C 6 -C 14 When aryl, said C 6 -C 14 Aryl is preferably phenyl, naphthyl, anthryl or phenanthryl.
When said R is 1-1 And R 1-2 Independently is C 6 -C 10 Aryl substituted C 6 -C 14 When aryl, said C 6 -C 10 Aryl is preferably phenyl or naphthyl. Said C 6 -C 14 Aryl is preferably phenyl, naphthyl, anthryl or phenanthryl.
When said R is 1 Is C 6 -C 14 When aryl, said C 6 -C 14 Aryl is preferably C 6 -C 10 Aryl, more preferably phenyl or naphthyl.
When said R is 1 Is represented by one or more R 2-1 Substituted C 6 -C 14 When aryl, said C 6 -C 14 Aryl is preferably C 6 -C 10 Aryl, more preferably phenyl or naphthyl.
When said R is 1 In the case of the "5-6 membered heteroaryl group having 1 to 3 hetero atoms and one or more hetero atoms selected from N, O and S", the "5-6 membered heteroaryl group having 1 to 3 hetero atoms and one or more hetero atoms selected from N, O and S" is preferably a "5-6 membered heteroaryl ring having 1 hetero atom and having N, O or S", and more preferably a pyridyl group
Figure BDA0002073604040000102
Figure BDA0002073604040000103
When said R is 1 Is represented by one or more R 2-2 When the substituted "hetero atom is one or more selected from N, O and S, and 5-6 membered heteroaryl having 1 to 3 hetero atoms", the "hetero atom is one or more selected from N, O and S, and 5-6 membered heteroaryl having 1 to 3 hetero atoms" is preferably "5-6 membered heteroaryl having N, O or S hetero atoms and 1 hetero atom".
When said R is 1 Is C 1 -C 10 When alkyl, said C 1 -C 10 The alkyl group is preferably C 1 -C 4 An alkyl group. Said C 1 -C 4 The alkyl group is preferably methyl, ethyl, n-propyl, iso-propylPropyl, n-butyl, isobutyl or tert-butyl.
When said R' is C 1 -C 4 When alkyl, said C 1 -C 4 The alkyl group is preferably a methyl group, an ethyl group, an n-oxy group, an isopropyl group, an n-butyl group, an isobutyl group or a tert-butyl group.
When said R is 2-1 And R 2-2 Independently halogen, the halogen is preferably fluorine, chlorine, bromine or iodine.
When said R is 2-1 And R 2-2 Independently is C 1 -C 10 When alkyl, said C 1 -C 10 The alkyl group is preferably C 1 -C 4 An alkyl group. Said C 1 -C 4 The alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a tert-butyl group.
When said R is 2-1 And R 2-2 Independently is C 1 -C 10 At alkoxy, said C 1 -C 10 Alkoxy is preferably C 1 -C 4 An alkoxy group. Said C 1 -C 4 The alkoxy group is preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy.
When said R is 2 Is C 1 -C 4 When alkyl, said C 1 -C 4 The alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a tert-butyl group.
When said ring C is C 6 -C 30 When it is an aromatic ring, said C 6 -C 30 The aromatic ring is preferably C 6 -C 14 Aromatic rings, for example, benzene, naphthalene, anthracene or phenanthrene rings.
When said ring C is substituted by one or more R 3-1 Substituted C 6 -C 30 When it is an aromatic ring, said C 6 -C 30 The aromatic ring is preferably C 6 -C 14 Aromatic rings, for example, benzene, naphthalene, anthracene or phenanthrene rings.
When said ring C is a "5-to 14-membered heteroaromatic ring having 1 to 3 heteroatoms selected from one or more of N, O and S",the "heteroatom is selected from one or more of N, O and S, 5-14 membered heteroaromatic ring with 1-3 heteroatoms" is preferably "heteroatom is selected from one or more of N, O and S, 5-6 membered heteroaromatic ring with 1-3 heteroatoms" or "heteroatom is selected from one or more of N, O and S, 8-10 membered heteroaromatic ring with 1-3 heteroatoms". The "5-6 membered heteroaromatic ring having 1 to 3 hetero atoms and being selected from one or more of N, O and S" is preferably "5-6 membered heteroaromatic ring having N, O hetero atoms or S hetero atoms and 1 hetero atom", and is more preferably a thiophene ring (for example,
Figure BDA0002073604040000121
) Or a pyridine ring (for example,
Figure BDA0002073604040000122
). The "hetero atom is one or more selected from N, O and S, and the 8-to 10-membered heteroaromatic ring having 1 to 3 hetero atoms" is preferably "an 8-to 10-membered heteroaromatic ring having N, O or S hetero atoms and 1 hetero atom", "an 8-to 10-membered heteroaromatic ring having N, O or S hetero atoms and 2 hetero atoms" or "an 8-to 10-membered heteroaromatic ring having N, O and S hetero atoms and 2 hetero atoms". The "8-to 10-membered heteroaromatic ring having N, O or S as a heteroatom and 1 as a heteroatom" is preferably a quinoline ring (for example,
Figure BDA0002073604040000123
) An isoquinoline ring, a benzofuran ring (e.g.,
Figure BDA0002073604040000124
) Or a benzothiophene ring (for example,
Figure BDA0002073604040000125
). The "8-to 10-membered heteroaromatic ring having N, O or S as a heteroatom and 2 as a heteroatom" is preferably a quinoxaline ring (for example,
Figure BDA0002073604040000126
). Said "contains two heteroatoms of N, O and SAnd the 8-to 10-membered heteroaromatic ring "having 2 hetero atoms is preferably a benzothiazole ring.
When the ring C is a "5-to 14-membered heteroaromatic ring having 1 to 3 heteroatoms selected from one or more of N, O and S", the "heteroatom is one or more of N, O and S", and the "5-to 14-membered heteroaromatic ring having 1 to 3 heteroatoms" is preferably a "heteroatom selected from one or more of N, O and S, a 5-to 6-membered heteroaromatic ring having 1 to 3 heteroatoms" or a "heteroatom selected from one or more of N, O and S, and an 8-to 10-membered heteroaromatic ring having 1 to 3 heteroatoms". The "5-6 membered heteroaromatic ring having 1 to 3 hetero atoms and one or more hetero atoms selected from N, O and S" is preferably "5-6 membered heteroaromatic ring having 1 hetero atom and N, O or S". The "hetero atom is one or more selected from N, O and S, and the 8-to 10-membered heteroaryl ring having 1 to 3 hetero atoms" is preferably "an 8-to 10-membered heteroaryl ring having N, O or S as a hetero atom and 1 hetero atom", "an 8-to 10-membered heteroaryl ring having N, O or S as a hetero atom and 2 hetero atoms" or "an 8-to 10-membered heteroaryl ring having N, O and S as both hetero atoms and 2 hetero atoms".
When said R is 3-1 And R 3-2 Independently halogen, the halogen is preferably fluorine, chlorine, bromine or iodine.
When said R is 3-1 And R 3-2 Independently is C 1 -C 10 When alkyl, said C 1 -C 10 The alkyl group is preferably C 1 -C 4 Alkyl groups, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl.
When said R is 3-1 And R 3-2 Independently is C 1 -C 10 At alkoxy, said C 1 -C 10 Alkoxy is preferably C 1 -C 4 Alkoxy, for example methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy.
When said R is 3-1 And R 3-2 Independently is halo C 1 -C 4 When alkyl, said C 1 -C 4 Alkyl radical is excellentSelected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl; the halo is preferably substituted by fluoro, chloro, bromo or iodo. Said halo C 1 -C 4 Alkyl is preferably halo C 1 -C 2 Alkyl, more preferably fluoro C 1 -C 2 Alkyl, most preferably trifluoromethyl.
When said R is 3-1 And R 3-2 Independently is C 1 -C 10 When the mercapto group is substituted by an alkyl group, said C 1 -C 10 The alkyl group is preferably C 1 -C 4 Alkyl groups, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl.
When said R is d 、R e And R f Independently is C 1 -C 4 When alkyl, said C 1 -C 4 The alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a tert-butyl group.
When R' "is C 1 -C 4 When alkyl, said C 1 -C 4 The alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a tert-butyl group.
When R' "is C 1 -C 4 At alkoxy, said C 1 -C 4 The alkoxy group is preferably methoxy, ethoxy, n-oxopropyl, i-oxopropyl, n-butoxy, i-butoxy or tert-butoxy
When said R is 3-1 And R 3-2 When the "5-6 membered heteroaryl group having 1 to 3 hetero atoms and one or more hetero atoms selected from N, O and S" are independent, the "5-6 membered heteroaryl group having 1 to 3 hetero atoms and one or more hetero atoms selected from N, O and S" is preferably the "5-6 membered heteroaryl group having 1 hetero atom to 1 hetero atom of N, O or S", and is more preferably a pyridyl group (for example,
Figure BDA0002073604040000131
)。
when said R is 3-1 And R 3-2 Independently is C 6 -C 14 Aryl is said to C 6 -C 14 Aryl is preferably phenyl, naphthyl, anthryl or phenanthryl.
When said R is 3-1 And R 3-2 Independently is C 6 -C 10 Aryl substituted C 6 -C 14 When aryl, said C 6 -C 10 Aryl is preferably phenyl or naphthyl. Said C 6 -C 14 Aryl is preferably phenyl, naphthyl, anthryl or phenanthryl.
In ring C, when with R 3 Of the carbon bound to R 4 Steric hindrance is preferably considered when the steric hindrance and the acidity of the attached carbon are different in magnitude. When with R 3 The carbon attached being more sterically hindered than R 4 Steric hindrance of the carbon to which it is attached, preferably with R 4 The attached carbons react and vice versa. For example, when the compound II is
Figure BDA0002073604040000141
When the carbon in the para-position to t-Bu preferentially participates in the reaction, and the compound II is
Figure BDA0002073604040000142
In this case, the carbon atoms in the ortho-and para-positions of Me have equal opportunities to participate in the reaction.
In ring C, when with R 3 Of the carbon bound to R 4 Steric hindrance of the attached carbon equivalent to R 3 The carbon to which it is attached is more acidic than R 4 Acidity of the carbon to which it is attached, preferably with R 3 The attached carbons react and vice versa.
In ring C, when R is 3 Compared with R 4 In the case of a readily removable substituent, the substituent is preferably bonded to R 3 The attached carbons react and vice versa. The leaving priority of the easy-leaving substituent group is OTf > D > H.
Preferably, R is 1 Is any one of the following structures:
Figure BDA0002073604040000143
preferably, R is 2 Is hydrogenOr a methyl group.
In a preferred embodiment, when said compound I is
Figure BDA0002073604040000151
When the ring B in the compound II is C 6 -C 14 Aryl rings or, substituted by one or more R 1-1 Substituted C 6 -C 14 An aromatic ring; x is bromine; said R 1-1 Is halogen, C 1 -C 4 Alkyl radical, C 1 -C 4 Alkoxy radical D, C 1 -C 4 An alkyl-substituted mercapto group,
Figure BDA0002073604040000152
And C 6 -C 10 Aryl substituted C 6 -C 14 One or more of aryl groups. The ring B is preferably C 6 -C 14 The aromatic ring is more preferably a benzene ring.
In a preferred embodiment, when said compound II is
Figure BDA0002073604040000153
When the compound I is shown in the specification, the ring A in the compound I is a benzene ring or substituted by one or more R 1-1 A substituted benzene ring, or, a pyridine ring; r in the compound I 1 Is C 6 -C 10 Aryl or, R 2-1 Substituted C 6 -C 10 Aryl radical, C 1 -C 4 Alkoxy-substituted pyridyl, C 1 -C 4 Alkyl or
Figure BDA0002073604040000154
R in the compound I 2 Is C 1 -C 4 Alkyl or hydrogen; said R 1-1 Selected from halogen, fluoro C 1-2 Alkyl radical, C 1 -C 4 Alkyl or C 1 -C 4 An alkoxy group; r is as described 2 -1 Selected from halogen, C 1 -C 4 Alkyl radical, C 1 -C 4 Alkoxy and C 1 -C 2 A haloalkyl group. The pyridine ring is preferably
Figure BDA0002073604040000155
Said R 1 Preferably C 1 -C 4 An alkyl group. Said R 2 Hydrogen is preferred.
When the compound I is
Figure BDA0002073604040000156
When the compound II is represented by the following structure:
Figure BDA0002073604040000157
Figure BDA0002073604040000161
when the compound II is
Figure BDA0002073604040000162
When the compound I is represented by the formula, the compound I is preferably represented by any one of the following structures:
Figure BDA0002073604040000163
preferably, the compound I is of any one of the following structures:
Figure BDA0002073604040000171
preferably, the compound II is of any one of the following structures:
Figure BDA0002073604040000181
the solvent may be a conventional solvent in the art for carrying out such a reaction, and is preferably an ether-type solvent. The ether solvent is preferably 1, 4-dioxane. The solvent may be used in an amount conventional in the art for carrying out such reactions, preferably in a volume molar ratio to compound I of from 1 to 10L/mol, more preferably from 3 to 8L/mol, for example 5.0L/mol.
The palladium acetate may be used in an amount conventionally used in the art for carrying out such a reaction, and preferably is used in a molar ratio to the compound I of 0.01 to 0.10, more preferably 0.03 to 0.06, for example, 0.05.
The ligand is preferably
Figure BDA0002073604040000182
The ligand may be used in an amount conventional in the art for carrying out such reactions, preferably in a molar ratio to compound I of from 0.05 to 0.4, more preferably from 0.1 to 0.3, e.g. 0.1 or 0.2.
The base may be a conventional base used in the art to carry out such reactions, preferably one or more of an alkali metal acetate, an alkali metal hydroxide, an alkali metal carbonate and an alkali metal PivO-acid salt. The acetate of the alkali metal is preferably one or more of potassium acetate, sodium acetate and cesium acetate. The alkali metal hydroxide is preferably one or more of potassium hydroxide, sodium hydroxide and cesium hydroxide. The carbonate of the alkali metal is preferably one or more of potassium carbonate, sodium carbonate and cesium carbonate. The PivO acid salt of the alkali metal is preferably one or more of potassium PivO acid, sodium PivO acid and cesium PivO acid. The base may be used in an amount conventional in the art for carrying out such reactions, preferably in a molar ratio to compound I of from 0.5 to 4, more preferably from 1 to 3, e.g. 2.0.
The amount of compound II to be used may be that conventionally used in the art for carrying out such reactions, and is preferably in a molar ratio to compound I of from 1 to 4, more preferably from 1 to 2, e.g. 1.5.
The reaction temperature is a temperature which is conventional for such reactions, preferably 90-170 ℃, more preferably 110-160 ℃, e.g., 130 ℃ or 150 ℃.
The reaction is preferably carried out under anhydrous conditions.
The progress of the reaction can be monitored by monitoring methods customary in the art (e.g., TLC, HPLC or NMR), and is generally at the end of the reaction when compound I disappears. The reaction time is preferably 2 to 8 hours, for example, 5 hours.
After the reaction is finished, the method also can comprise the operation of post-treatment. The work-up procedure is a conventional work-up procedure for such reactions, preferably comprising the steps of: and concentrating and purifying the reaction solution after the reaction is finished.
In a preferred embodiment of the present invention, the solvent is an ether solvent; the volume mol ratio of the solvent to the compound I is 3-8L/mol; the molar ratio of the palladium acetate to the compound I is 0.03-0.06; the ligand is
Figure BDA0002073604040000191
The molar ratio of the ligand to the compound I is 0.1-0.3; the alkali is one or more of acetate of alkali metal, hydroxide of alkali metal, carbonate of alkali metal and PivO acid salt of alkali metal; the acetate of the alkali metal is preferably one or more of potassium acetate, sodium acetate and cesium acetate; the hydroxide of the alkali metal is preferably one or more of potassium hydroxide, sodium hydroxide and cesium hydroxide; the carbonate of the alkali metal is preferably one or more of potassium carbonate, sodium carbonate and cesium carbonate; the PivO acid salt of the alkali metal is preferably one or more of potassium PivO acid, sodium PivO acid and cesium PivO acid; the molar ratio of the alkali to the compound I is 1-3; the molar ratio of the compound II to the compound I is 1-2; the reaction temperature is 110-160 ℃; the reaction is carried out under anhydrous conditions.
In a more preferred embodiment of the invention, the ligand is DPEPhos, the base is potassium carbonate, and the compound I is
Figure BDA0002073604040000201
The compound II is
Figure BDA0002073604040000202
The invention also provides a fused ring compound, which has the following structure:
Figure BDA0002073604040000203
Figure BDA0002073604040000211
the above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.
The term "halo" or "halogen" refers to-Cl, -Br, -I, or-F.
In the present invention, the group not particularly specified as substituted or unsubstituted means a group not substituted by a substituent, for example, "C 1 -C 10 Alkyl "refers to C unsubstituted by a substituent 1 -C 10 The alkyl group specifically includes methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and the like.
In the invention, the preparation method of the compound I can be referred to Chin.J.chem.2018,36, 743-748, and other reagents and raw materials used are commercially available.
In the invention, the room temperature is 0-35 ℃, preferably 10-30 ℃;
in the invention, the DPEPhos is bis (2-diphenylphosphinophenyl) ether (CAS: 166330-10-5), and the PivO acid is pivalic acid.
In the present invention,
Figure BDA0002073604040000212
represents R 2 And R 1 The double bonds between the two are in E and/or Z configuration, the products corresponding to the E or Z configuration are the same, and the same products can be obtained when the double bonds are in the E and Z configurations.
In the present invention, the ortho position of X means a substituent on the carbon adjacent to the carbon to which X is attached (for example,
Figure BDA0002073604040000213
in (e), the ortho position to X is F); the meta position of X refers to a substituent on the carbon meta to the carbon to which X is attached (e.g.,
Figure BDA0002073604040000214
in (b), the meta position of X is methyl).
The positive progress effects of the invention are as follows: the preparation method has good compatibility to substrates, can obtain a plurality of condensed ring aromatic compounds in a short time by convergent synthesis, and particularly shows extremely excellent regioselectivity for condensed ring aromatic hydrocarbons containing heteroatoms.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the invention thereto. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1 examination of substrate compatibility
Figure BDA0002073604040000221
In a dry sealed tube, 3.4mg Pd (OAc) is added respectively under the protection of argon 2 ，16.2mg DPEPhos，77.4mg 1a(0.3mmol)，47.1μL 2a(0.45mmol)，82.8mg K 2 CO 3 1.5mL of dioxane, warmed to 130 ℃ and stirred for 5 h. Cooled to room temperature, concentrated and the residue was column chromatographed using n-hexane as eluent to give 65mg of 3aa white solid in 85% yield.
1 H NMR(400MHz,CDCl 3 )δ8.77(d,J＝8.0Hz,1H),8.72(d,J＝8.4Hz,1H),7.92-7.88(m,2H),7.68-7.59(m,4H),7.56-7.43(m,6H)ppm；EI-MS m/z(％):254.1(M + )；
The substrate 1a was changed, keeping compound 2a unchanged at 130 ℃, otherwise as in the above example, with the following products and yields as in table 1 below:
Figure BDA0002073604040000222
Figure BDA0002073604040000231
Figure BDA0002073604040000241
Figure BDA0002073604040000251
the substrate 2a was changed, keeping compound 1a unchanged at 130 ℃, otherwise as in the above example, with the following products and yields in table 2:
TABLE 2
Figure BDA0002073604040000252
Figure BDA0002073604040000261
Figure BDA0002073604040000271
Figure BDA0002073604040000272
In a dry sealed tube, 3.4mg Pd (OAc) is added respectively under the protection of argon 2 ，16.2mg DPEPhos，77.4mg 1a(0.3mmol)，93.1mg 2n(0.45mmol)，82.8mg K 2 CO 3 1.5mL of dioxane, warmed to 130 ℃ and stirred for 5 h. Cooled to room temperature, concentrated, and the residue was subjected to column chromatography using n-hexane as an eluent to collect a band of the product, to obtain 28mg of a 3an white solid in a yield of 31%.
In a dry sealed tube, 3.4mg Pd (OAc) is added respectively under the protection of argon 2 ，16.2mg DPEPhos，77.4mg 1a(0.3mmol)，93.1mg 2n(0.45mmol)，82.8mg K 2 CO 3 ，15mL of dioxane was heated to 150 ℃ and stirred for 5 h. Cooled to room temperature, concentrated, and the residue was subjected to column chromatography using n-hexane as an eluent to collect a band of the product, to give 50mg of 3an of a white solid in 55% yield.
1 H NMR(400MHz,CDCl 3 )δ8.82(d,J＝8.4Hz,1H),8.74-8.70(m,2H),8.63(s,1H),8.02-7.96(m,3H),7.70-7.46(m,9H)ppm；EI-MS m/z(％):304.1(M + )；
The substrate 2n was changed, keeping compound 1a unchanged at 150 ℃, otherwise as in the above example, with the following products and yields in table 3:
TABLE 3
Figure BDA0002073604040000281
Figure BDA0002073604040000291
Figure BDA0002073604040000301
2. Screening for ligands
Figure BDA0002073604040000302
In the reaction formula, ligand is ligand and dioxane is 1, 4-dioxane.
Reaction conditions are as follows:
compound 1(0.2mmol,1.0eq), Compound 2(1.5eq), Pd (OAc) 2 (0.05eq), ligand (0.1 or 0.2eq), K 2 CO 3 (2.0eq), 1, 4-dioxane (1.0mL)
3. Screening for bases
Figure BDA0002073604040000311
Figure BDA0002073604040000312
Identification data of compounds:
Figure BDA0002073604040000313
1 H NMR(400MHz,CDCl 3 )δ8.77(d,J＝8.0Hz,1H),8.72(d,J＝8.4Hz,1H),7.92-7.88(m,2H),7.68-7.59(m,4H),7.56-7.43(m,6H)ppm；EI-MS m/z(％):254.1[M] + .
Figure BDA0002073604040000314
1 H NMR(400MHz,CDCl 3 )δ8.77(d,J＝8.0Hz,1H),7.92-7.88(m,2H),7.68-7.59(m,3H),7.56-7.43(m,4H)ppm；EI-MS m/z(％):254.1[M] + .
Figure BDA0002073604040000321
1 H NMR(400 MHz,CDCl 3 )δ8.69-8.65(m,2H),7.86(d,J＝8.0Hz,1H),7.68-7.62(m,3H),7.59-7.46(m,7H),2.47(s,3H)ppm；EI-MS m/z(％):268.1[M] + .
Figure BDA0002073604040000322
1 H NMR(400MHz,CDCl 3 )δ8.69(d,J＝8.0Hz,1H),8.54(s,1H),7.85(d,J＝8.0Hz,1H),7.80(d,J＝8.4Hz,1H),7.64-7.59(m,3H),7.57-7.47(m,4H),7.45-7.41(m,1H),7.34(d,J＝8.4Hz,1H),2.60(s,3H)ppm；EI-MS m/z(％):268.1[M] + .
Figure BDA0002073604040000323
1 H NMR(400MHz,CDCl 3 )δ8.56(d,J＝8.0Hz,1H),8.37-8.33(m,1H),7.90-7.87(m,2H),7.67-7.61(m,3H),7.51-7.44(m,5H),7.28-7.24(m,1H)ppm；EI-MS m/z(％):272.1[M] + .
Figure BDA0002073604040000324
1 H NMR(400MHz,CDCl 3 )δ8.71(d,J＝2.4Hz,1H),8.61(d,J＝8.0Hz,1H),7.89-7.86(m,1H),7.83(d,J＝8.8Hz,1H),7.69-7.61(m,3H),7.51-7.45(m,6H)ppm；EI-MS m/z(％):288.0[M] + .
Figure BDA0002073604040000325
1 H NMR(400MHz,CDCl 3 )δ9.01(s,1H),8.68(d,J＝8.0Hz,1H),8.00(d,J＝8.0Hz,1H),7.87(d,J＝8.0Hz,1H),7.75(s,1H),7.70-7.61(m,3H),7.53-7.44(m,5H)ppm；EI-MS m/z(％):322.1[M] + .
Figure BDA0002073604040000331
1 H NMR(400MHz,CDCl 3 )δ10.12(s,1H),8.84(d,J＝8.0Hz,1H),8.66(d,J＝5.4Hz,1H),7.94(d,J＝8.0Hz,1H),7.89(s,1H),7.78-7.74(m,2H),7.70-7.66(m,1H),7.56-7.46(m,5H)ppm；EI-MS m/z(％):255.1[M] + .
Figure BDA0002073604040000332
1 H NMR(400MHz,CDCl 3 )δ9.11(t,J＝8.8Hz,2H),8.02-7.98(m,2H),7.85-7.78(m,3H),7.69-7.60(m,4H),7.56-7.44(m,5H)ppm； 13 C NMR(100MHz,CDCl 3 )δ140.94,138.65,133.17,132.84,130.39,130.25,129.77,129.59,128.50,128.48,128.35,128.24,128.18,128.10,128.08,127.43,126.98,126.22,126.11,126.05,126.02,124.68ppm；DART-MS m/z(％):305.1[M+H] + ；HRMS(EI)m/z:[M] + calculated value C 24 H 16 + 304.1252, found 304.1244.
Figure BDA0002073604040000333
1 H NMR(400MHz,CDCl 3 )δ8.75(d,J＝8.0Hz,1H),8.72(d,J＝8.0Hz,1H),7.86(d,J＝8.4Hz,1H),7.68-7.59(m,4H),7.51-7.45(m,2H),7.39-7.30(m,4H),2.06(s,3H)ppm；EI-MS m/z(％):268.1[M] + .
Figure BDA0002073604040000334
1 H NMR(400MHz,CDCl 3 )δ8.81(d,J＝8.0Hz,1H),8.75(d,J＝8.0Hz,1H),7.98(d,J＝8.0Hz,1H),7.92(d,J＝8.0Hz,1H),7.72-7.63(m,4H),7.59-7.55(m,1H),7.46-7.38(m,3H),7.32-7.30(m,1H),2.50(s,3H)ppm；EI-MS m/z(％):268.1[M] + .
Figure BDA0002073604040000341
1 H NMR(400MHz,CDCl 3 )δ8.75(d,J＝8.0Hz,1H),8.69(d,J＝8.0Hz,1H),7.93(d,J＝8.0Hz,1H),7.86(d,J＝8.0Hz,1H),7.66-7.57(m,4H),7.53-7.49(m,1H),7.44-7.42(m,2H),7.32-7.30(m,2H),2.46(s,3H)ppm；EI-MS m/z(％):268.1[M] + .
Figure BDA0002073604040000342
1 H NMR(400MHz,CDCl 3 )δ8.76(d,J＝8.0Hz,1H),8.70(d,J＝8.0Hz,1H),7.88-7.84(m,2H),7.68-7.59(m,4H),7.55-7.47(m,3H),7.22-7.17(m,2H)ppm；EI-MS m/z(％):272.1[M] + .
Figure BDA0002073604040000343
1 H NMR(400MHz,CDCl 3 )δ8.74(d,J＝8.0Hz,1H),8.68(d,J＝8.0Hz,1H),7.64-7.57(m,4H),7.53-7.49(m,1H),7.47-7.42(m,4H)ppm；EI-MS m/z(％):288.1[M] + .
Figure BDA0002073604040000344
1 H NMR(400MHz,CDCl 3 )δ8.82-8.78(m,2H),7.99-7.95(m,2H),7.90(d,J＝8.0Hz,1H),7.78(s,1H),7.74-7.70(m,1H),7.66-7.55(m,4H),7.49-7.37(m,4H),7.29-7.20(m,1H)ppm；EI-MS m/z(％):304.1[M] + .
Figure BDA0002073604040000351
1 H NMR(400MHz,CDCl 3 )δ8.78(d,J＝8.0Hz,1H),8.72(d,J＝8.0Hz,1H),8.33(d,J＝2.0Hz,1H),7.89(t,J＝8.4Hz,2H),7.77-7.74(m,1H),7.71-7.60(m,4H),7.58-7.54(m,1H),6.88(d,J＝8.4Hz,1H),4.47(q,J＝6.8Hz,2H),1.48(t,J＝6.8Hz,3H)ppm； 13 C NMR(100MHz,CDCl 3 )δ163.39,147.33,140.39,135.05,131.47,131.19,130.72,130.09,129.33,128.70,128.02,126.99,126.84,126.73,126.67,126.49,123.07,122.59,110.48,61.93,14.82ppm；DART-MS m/z(％):300.1[M+H] + ；HRMS(DART)m/z:[M] + Calculated value C 21 H 17 NO + 299.1310, found 299.1313.
Figure BDA0002073604040000352
1 H NMR(400MHz,CDCl 3 )δ8.73(d,J＝9.6Hz,1H),8.66(d,J＝7.6Hz,1H),8.08-8.05(m,1H),7.82-7.80(m,1H),7.69-7.63(m,2H),7.62-7.54(m,3H),2.74(s,3H)ppm；EI-MS m/z(％):192.1[M] + .
Figure BDA0002073604040000353
1 H NMR(400MHz,CDCl 3 )δ8.76-8.74(m,1H),8.66-8.64(m,1H),8.21-8.18(m,1H),7.87-7.84(m,1H),7.67-7.55(m,5H),3.80-3.69(m,1H),1.47(d,J＝6.8Hz,6H)ppm；EI-MS m/z(％):220.1[M] + .
Figure BDA0002073604040000361
1 H NMR(400MHz,CDCl 3 )δ8.93-8.91(m,1H),8.74-8.71(m,1H),8.68(d,J＝8.0Hz,1H),8.47(s,1H),7.96(d,J＝8.0Hz,1H),7.76-7.61(m,4H),4.04(s,3H)ppm；EI-MS m/z(％):236.1[M] + .
Figure BDA0002073604040000362
1 H NMR(400MHz,CDCl 3 )δ8.72-8.70(m,2H),8.13-8.11(m,2H),7.64-7.58(m,4H),2.73(s,6H)ppm；EI-MS m/z(％):206.1[M] + .
Figure BDA0002073604040000363
1 H NMR(400MHz,CDCl 3 )δ8.79-8.77(m,1H),8.73(d,J＝8.4Hz,1H),8.17-8.14(m,1H),7.71-7.65(m,2H),7.59-7.50(m,3H),7.47-7.36(m,3H),7.31-7.30(m,2H),2.46(s,3H)ppm；EI-MS m/z(％):268.1[M] + .
Figure BDA0002073604040000364
1 H NMR(400MHz,CDCl 3 )8.79(d,J＝8.4Hz,1H),8.62(d,J＝8.4Hz,1H),7.91(d,J＝8.0Hz,1H),7.87(s,1H),7.68-7.64(m,1H),7.57-7.50(m,6H),7.48-7.45(m,2H),2.74(s,3H)ppm； 13 C NMR(100MHz,CDCl 3 )δ141.31,138.56,135.04,131.00,130.75,130.29,130.21,130.03,128.34,128.07,127.38,126.89,126.47,126.38,126.22,123.69,123.24,120.78,20.01ppm；EI-MS m/z(％):268.2[M] + ；HRMS(EI)m/z:[M] + Calculated value C 21 H 16 + 268.1252, found 268.1260.
Figure BDA0002073604040000365
1 H NMR(400MHz,CDCl 3 )8.94(d,J＝8.4Hz,0.55H,3ac’),8.70(d,J＝8.4Hz,0.45H,3ac),8.58(d,J＝8.4Hz,0.45H,3ac),7.94(d,J＝8.4Hz,0.55H,3ac’),7.88(d,J＝8.4Hz,0.45H,3ac),7.56-7.54(m,0.55H,3ac’),7.65-7.60(m,2.45H,3ac+3ac’),7.54-7.41(m,7.55H,3ac+3ac’),3.16(s,1.65H,3ac’),2.54(s,1.35H,3ac)ppm； 13 C NMR(100MHz,CDCl 3 )140.95,140.86,138.77,138.45,136.62,135.19,133.16,132.46,132.00,131.72,131.29,130.79,130.68,130.09,130.05,129.87,128.64,128.41,128.35,128.30,128.21,127.85,127.65,127.56,127.34,127.32,126.89,126.87,126.39,126.19,126.07,125.77,125.33,122.72,122.47,27.33,21.53ppm；DART-MS m/z(％):268.1[M] + ；HRMS(DART)m/z:[M+H] + Calculated value C 21 H 17 + 269.1325, found 269.1324.
Figure BDA0002073604040000371
1 H NMR(400MHz,CDCl 3 )8.74(d,J＝8.4Hz,1H),8.65(d,J＝8.4Hz,1H),7.989(d,J＝8.0Hz,1H),7.85-7.84(m,1H),7.76-7.73(m,1H),7.68(s,1H),7.66-7.62(m,1H),7.55-7.48(m,5H),7.47-7.43(m,1H),1.46(s,9H)ppm； 13 C NMR(100MHz,CDCl 3 )δ149.79,140.99,138.71,131.44,130.91,130.57,130.10,128.29,127.88,127.82,127.30,126.87,126.36,126.11,124.98,124.32,122.78,122.39,34.84,31.43ppm；DART-MS m/z(％):310.2[M] + ；HRMS(EI)m/z:[M] + Calculated value C 24 H 22 + 310.1722, found 310.1726.
Figure BDA0002073604040000372
1 H NMR(400MHz,CDCl 3 )8.76(d,J＝8.4Hz,1H),8.51(s,1H),7.90(d,J＝7.6Hz,1H),7.78(d,J＝8.0Hz,1H),7.66-7.62(m,2H),7.55-7.48(m,5H),7.46-7.43(m,2H),2.64(s,3H)ppm；EI-MS m/z(％):268.1[M] + .
Figure BDA0002073604040000381
1 H NMR(400MHz,CDCl 3 )8.69(d,J＝8.4Hz,1H),8.08(d,J＝2.4Hz,1H),7.91(d,J＝8.0Hz,1H),7.80(d,J＝8.4Hz,1H),7.66-7.62(m,2H),7.55-7.48(m,5H),7.47-7.42(m,1H),7.27-7.24(m,1H),4.03(s,3H)ppm；EI-MS m/z(％):284.1[M] + .The data is consistent with the literature. 18
Figure BDA0002073604040000382
1 H NMR(400MHz,CDCl 3 )δ8.73(d,J＝8.4Hz,1H),8.55(s,1H),7.91(d,J＝8.0Hz,1H),7.80(d,J＝8.4Hz,1H),7.68-7.62(m,2H),7.55-7.43(m,7H),2.68(s,3H)ppm； 13 C NMR(100MHz,CDCl 3 )δ140.74,138.23,136.88,131.47,130.38,130.08,129.81,129.31,129.06,128.35,127.40,127.16,126.98,126.78,126.46,126.16,122.87,119.86,16.40ppm；EI-MS m/z(％):300.1[M] + ；HRMS(EI)m/z:[M] + Calculated value C 21 H 16 S + 300.0973, found 300.0981.
Figure BDA0002073604040000383
1 H NMR(400MHz,CDCl 3 )δ8.90(s,1H),8.85(d,J＝8.4Hz,1H),7.92-7.86(m,2H),7.76-7.74(m,1H),7.70-7.66(m,2H),7.55-7.44(m,6H),0.42(s,9H)ppm； 13 C NMR(100MHz,CDCl 3 )δ140.87,139.19,138.66,131.86,131.30,131.25,130.65,130.09,129.10,128.33,127.78,127.75,127.49,127.39,126.99,126.47,126.44,122.79,-0.84ppm；EI-MS m/z(％):326.1[M] + ；HRMS(EI)m/z:[M] + Calculated value C 23 H 22 Si + 326.1491, found 326.1497.
Figure BDA0002073604040000391
1 H NMR(400MHz,CDCl 3 )8.68-8.66(m,2H),7.91(d,J＝8.4Hz,1H),7.81(d,J＝8.4Hz,1H),7.69-7.63(m,2H),7.57-7.46(m,7H)ppm； 13 C NMR(100MHz,CDCl 3 )δ140.45,139.16,132.57,131.40,131.05,130.05,130.01,129.86,129.69,128.40,127.56,127.39,127.16,127.05,126.80,126.78,122.98,122.31ppm；EI-MS m/z(％):288.1[M] + ；HRMS(EI)m/z:[M] + Calculated value C 20 H 13 Cl + 288.0706, found 288.0704.
Figure BDA0002073604040000392
1 H NMR(400MHz,CDCl 3 )8.98(s,1H),8.78(d,J＝8.0Hz,1H),7.98(d,J＝8.0Hz,1H),7.94(d,J＝8.0Hz,1H),7.80(d,J＝8.0Hz,1H),7.75-7.71(m,2H),7.61-7.57(m,1H),7.54-7.46(m,5H)ppm；EI-MS m/z(％):322.1[M] + .The data is consistent with the literature. 10
Figure BDA0002073604040000393
1 H NMR(400MHz,CDCl 3 )δ10.28(s,1H),9.21(s,1H),8.87(d,J＝8.40Hz,1H),8.09(dd,J＝8.4Hz,J＝1.6Hz,1H),8.04-7.95(m,2H),7.78-7.73(m,2H),7.63-7.59(m,1H),7.55-7.48(m,5H)ppm； 13 C NMR(100MHz,CDCl 3 )δ192.44,142.38,140.12,135.60,134.21,131.39,130.89,129.89,129.73,129.61,128.49,127.87,127.40,127.37,127.19,127.01,125.44,123.00ppm；DART-MS m/z(％):282.1[M] + ；HRMS(EI)m/z:[M] + Calculated value C 21 H 14 O + 282.1045, found 282.1043.
Figure BDA0002073604040000401
1 H NMR(400MHz,CDCl 3 )δ9.36(s,1H),8.87(d,J＝8.4Hz,1H),8.15(d,J＝8.4Hz,1H),7.95-7.92(m,2H),7.75-7.70(m,2H),7.60-7.49(m,6H),2.81(s,3H)ppm； 13 C NMR(100MHz,CDCl 3 )δ198.19,141.63,140.26,134.75,134.54,131.35,131.08,129.91,129.42,128.97,128.44,127.75,127.28,127.17,127.14,126.89,125.74,123.79,123.00,26.96ppm；DART-MS m/z(％):297.1[M+H] + ；HRMS(DART)m/z:[M+H] + Calculated value C 22 H 17 O + 297.1274, found 297.1273.
Figure BDA0002073604040000402
1 H NMR(400MHz,CDCl3)δ9.46(s,1H),8.86(d,J＝8.4Hz,1H),8.21(d,J＝8.4Hz,1H),7.93-7.89(m,2H),7.73-7.69(m,2H),7.58-7.46(m,6H),4.03(s,3H)ppm； 13 C NMR(100MHz,CDCl 3 )δ167.44,141.37,140.30,134.41,131.24,130.90,129.92,129.37,128.75,128.41,127.71,127.70,127.14,127.10,127.06,126.92,126.77,125.12,123.14,52.37ppm；DART-MS m/z(％):313.1[M+H] + ；HRMS(EI)m/z:[M] + Calculated value C 22 H 16 O 2 + 312.1150, found 312.1144.
Figure BDA0002073604040000403
1 H NMR(400MHz,CDCl 3 )δ8.82(d,J＝8.4Hz,1H),8.74-8.70(m,2H),8.63(s,1H),8.02-7.96(m,3H),7.70-7.46(m,9H)ppm； 13 C NMR(100MHz,CDCl 3 )δ141.27,139.26,132.31,131.00,130.88,130.55,130.29,128.60,128.40,127.82,127.69,127.47,127.38,126.90,126.70,126.56,126.46,126.34,123.42,123.20,122.29,121.09ppm；EI-MS m/z(％):304.1[M] + ；HRMS(EI)m/z:[M] + Calculated value C 24 H 16 + 304.1252, found 304.1248.
Figure BDA0002073604040000411
1 H NMR(400MHz,CDCl 3 )δ8.98(d,J＝8.8Hz,1H),8.92-8.90(m,1H),8.74-8.69(m,2H),8.65-8.63(m,1H),8.53(s,1H),8.03(d,J＝8.8Hz,1H),7.71-7.60(m,7H),7.59-7.47(m,4H)ppm； 13 C NMR(100MHz,CDCl 3 )δ140.93,139.44,132.21,130.96,130.67,130.19,130.14,129.70,129.45,129.30,128.78,128.50,127.54,127.43,127.37,127.22,126.81,126.66,126.42,126.20,125.96,125.87,123.78,123.56,123.18,121.66ppm；DART-MS m/z(％):354.2[M] + ；HRMS(DART)m/z:[M+H] + Calculated value C 28 H 19 + 355.1481, found 355.1479.
Figure BDA0002073604040000412
1 H NMR(400MHz,CDCl 3 )δ10.14(s,1H),8.94(d,J＝9.2Hz,1H),8.83(d,J＝8.4Hz,1H),8.73-8.72(m,2H),8.04(d,J＝8.4Hz,1H),7.95(d,J＝9.2Hz,1H),7.79(d,J＝5.6Hz,1H),7.77-7.73(m,1H),7.63-7.50(m,6H)ppm； 13 C NMR(100MHz,CDCl 3 )δ147.67,144.47,140.87,140.67,135.59,131.23,130.63,130.16,128.53,128.27,127.80,127.31,127.18,127.06,126.89,125.78,125.30,123.19,120.97,120.93ppm；EI-MS m/z(％):305.1[M] + ；HRMS(EI)m/z:[M] + Calculated value C 23 H 15 N + 305.1204, found 305.1196.
Figure BDA0002073604040000413
1 H NMR(400MHz,CDCl 3 )δ8.99-8.93(m,3H),8.82(d,J＝8.0Hz,1H),8.50(s,1H),8.24(d,J＝9.6Hz,1H),8.01(d,J＝8.0Hz,1H),7.73-7.70(m,1H),7.60-7.51(m,7H)ppm； 13 C NMR(100MHz,CDCl 3 )δ149.97,147.95,140.82,140.01,131.26,131.14,130.58,130.14,128.44,128.40,127.65,127.29,127.26,126.97,126.91,126.77,125.48,124.95,123.40,121.53,121.36ppm；EI-MS m/z(％):305.1[M] + ；HRMS(EI)m/z:[M] + Calculated value C 23 H 15 N + 305.1204, found 305.1207.
Figure BDA0002073604040000421
1 H NMR(400MHz,CDCl 3 )δ9.07(s,1H),8.80(d,J＝9.6Hz,2H),8.33(d,J＝9.2Hz,1H),7.96(d,J＝8.4Hz,1H),7.87(s,1H),7.72-7.69(m,1H),7.58-7.49(m,6H)ppm； 13 C NMR(100MHz,CDCl 3 )δ153.30,152.12,140.46,140.27,132.56,130.94,130.93,130.08,128.45,127.76,127.34,127.27,127.16,126.66,126.13,124.64,123.44,121.89,121.77ppm；DART-MS m/z(％):312.1[M+H] + ；HRMS(EI)m/z:[M] + Calculated value C 21 H 13 NS + 311.0769, found 311.0760.
Figure BDA0002073604040000422
1 H NMR(400MHz,CDCl 3 )δ9.42(s,1H),8.96(d,J＝8.0Hz,1H),8.81(d,J＝4.8Hz,1H),8.23(d,J＝8.0Hz,1H),8.00-7.93(m,3H),7.86-7.82(m,1H),7.72-7.68(m,2H),7.58-7.45(m,6H),7.32-7.26(m,1H)ppm； 13 C NMR(100MHz,CDCl 3 )δ157.64,149.92,140.76,139.53,137.36,136.93,131.98,131.39,131.00,130.19,130.08,129.16,128.37,127.48,127.21,127.04,126.72,126.61,125.45,123.29,122.25,121.30,121.00ppm；EI-MS m/z(％):331.1[M] + ；HRMS(EI)m/z:[M] + Calculated value C 25 H 17 N + 331.1361, found 331.1365.
Figure BDA0002073604040000423
1 H NMR(400MHz,CDCl 3 )δ11.01(d,J＝8.4Hz,1H),9.11(d,J＝1.6Hz,1H),8.94(d,J＝1.6Hz,1H),8.14(s,2H),8.05(d,J＝8.4Hz,1H),7.84-7.81(m,2H),7.64-7.49(m,6H)ppm； 13 C NMR(100MHz,CDCl 3 )δ143.46,143.19,142.95,142.29,140.45,133.20,132.62,132.36,131.94,130.22,130.12,128.42,128.27,127.72,127.50,127.45,126.91,126.64,125.36ppm；DART-MS m/z(％):307.1[M+H] + ；HRMS(DART)m/z:[M+H] + Calculated value C 22 H 15 N 2 + 307.1230, found 307.1230.
Figure BDA0002073604040000431
1 H NMR(400MHz,CDCl 3 )δ9.34(d,J＝8.4Hz,1H),8.99-8.97(m,1H),8.92(d,J＝8.4Hz,1H),8.16-8.14(m,1H),8.07-8.01(m,2H),7.70(s,1H),7.69-7.65(m,1H),7.58-7.50(m,6H),7.48-7.45(m,1H)ppm； 13 C NMR(100MHz,CDCl 3 )δ148.98,148.89,140.15,139.92,135.54,132.22,130.59,130.43,130.16,129.99,128.99,128.44,127.69,127.59,127.19,127.01,126.43,126.31,125.17,120.45ppm；EI-MS m/z(％):305.1[M] + ；HRMS(EI)m/z:[M] + Calculated value C 23 H 15 N + 305.1204, found 305.1207.
Figure BDA0002073604040000432
1 H NMR(400MHz,CDCl 3 )δ9.10(d,J＝8.4Hz,1H),8.01(d,J＝8.4Hz,1H),7.93(d,J＝2.4Hz,1H),7.86-7.83(m,4H),7.76-7.72(m,1H),7.60-7.51(m,5H),7.48-7.45(m,1H)ppm； 13 C NMR(100MHz,CDCl 3 )δ154.37,144.94,140.88,137.39,131.67,131.17,130.24,128.75,128.44,128.36,127.35,127.00,126.24,126.21,126.17,125.69,124.75,121.92,112.63,108.56ppm；DART-MS m/z(％):295.1[M+H] + ；HRMS(EI)m/z:[M] + Calculated value C 22 H 14 O + 294.1045, found 294.1040.
Figure BDA0002073604040000441
1 H NMR(400MHz,CDCl 3 )δ8.20(d,J＝8.0Hz,1H),7.92(d,J＝8.0Hz,1H),7.77(s,1H),7.59-7.56(m,1H),7.53-7.42(m,8H)ppm； 13 C NMR(100MHz,CDCl 3 )δ140.85,137.75,137.00,136.86,130.28,129.48,129.24,128.30,127.36,127.29,126.55,125.64,125.47,125.25,124.00,122.88ppm；EI-MS m/z(％):260.1[M] + ；HRMS(EI)m/z:[M] + Calculated value C 18 H 12 S + 260.0660, found 260.0657.
Figure BDA0002073604040000442
1 H NMR(400MHz,CDCl 3 )δ9.27(s,1H),8.77(d,J＝6.0Hz,2H),8.46(d,J＝8.4Hz,1H),7.97(d,J＝8.4Hz,1H),7.76-7.73(m,2H),7.69-7.65(m,1H),7.55-7.48(m,5H)ppm； 13 C NMR(100MHz,CDCl 3 )δ151.93,145.14,140.52,140.05,134.50,132.76,129.96,128.86,128.73,128.51,127.81,127.24,127.09,126.66,125.14,123.51,115.91ppm；EI-MS m/z(％):255.1[M] + ；HRMS(EI)m/z:[M] + Calculated value C 19 H 13 N + 255.1048, found 255.1046.
Figure BDA0002073604040000443
1 H NMR(400MHz,CDCl 3 )δ9.36(s,1H),9.26(d,J＝8.4Hz,1H),9.11(d,J＝8.4Hz,1H),8.34(d,J＝8.4Hz,1H),8.12(d,J＝8.4Hz,1H),7.90(s,1H),7.84-7.75(m,3H),7.71-7.67(m,1H),7.61-7.48(m,5H)ppm； 13 C NMR(100MHz,CDCl 3 )152.69,146.68,140.61,139.93,134.01,130.70,130.37,130.03,129.50,128.59,128.49,128.26,127.93,127.84,127.21,127.01,127.00,126.85,125.59,124.72,124.36ppm；EI-MS m/z(％):305.1[M] + ；HRMS(EI)m/z:[M] + Calculated value C 23 H 15 N + 305.1204, found 305.1200.
Figure BDA0002073604040000451
1 H NMR(400MHz,CDCl 3 )δ8.86(s,1H),8.70(d,J＝8.0Hz,1H),8.14(d,J＝4.8Hz,1H),7.98(d,J＝8.0Hz,1H),7.87(s,1H),7.77-7.74(m,5H),7.64-7.62(m,4H),7.59-7.48(m,8H),7.37-7.30(m,4H)ppm； 13 C NMR(100MHz,CDCl 3 )δ140.84,139.26,139.11,137.45,137.43,137.24,131.50,131.39,130.89,130.60,130.28,130.21,130.15,130.10,130.03,129.98,128.79,128.50,128.45,127.81,127.57,127.53,127.38,127.10,126.81,126.63,125.43,125.25,125.14,123.15ppm；EI-MS m/z(％):506.3[M] + ；HRMS(EI)m/z:[M] + Calculated value C 40 H 26 + 506.2035, found 506.2033.

Claims (20)

1. A preparation method of a fused ring compound III is characterized by comprising the following steps: in a solvent, in the presence of palladium acetate, alkali and a ligand, carrying out the reaction shown as the following on a compound I and a compound II to obtain a compound III;
the ligand is
Figure FDA0003710573740000011
HPCy 3 BF 4 、
Figure FDA0003710573740000012
Figure FDA0003710573740000013
R is H or 4-OMe;
the alkali is one or more of acetate, carbonate and PivO acid salt of alkali metal;
Figure FDA0003710573740000014
x is bromo, chloro or trifluoromethanesulfonyl;
Figure FDA0003710573740000017
and
Figure FDA0003710573740000018
independently a single or double bond;
Figure FDA0003710573740000015
represents R 2 And R 1 The double bond between them is in E and/or Z configuration;
ring A and ring B are independently C 6 -C 30 Aromatic ring, by one or more R 1-1 Substituted C 6 -C 30 An aromatic ring, a 5-to 14-membered heteroaromatic ring having one or more heteroatoms selected from N, O and S and 1-3 heteroatoms, or substituted with one or more R 1-2 Substituted "5-14 membered heteroaromatic ring with 1-3 heteroatoms selected from one or more of N, O and S;
R 1-1 and R 1-2 Independently selected from the following substituents: halogen, C 1 -C 10 Alkyl radical, C 1 -C 10 Alkoxy, D, trifluoromethanesulfonyl, halo C 1 -C 4 Alkyl radical, C 1 -C 10 An alkyl-substituted mercapto group,
Figure FDA0003710573740000016
"5-6 membered heteroaryl group containing 1 to 3 hetero atoms selected from N, O and S, one or more hetero atoms 6 -C 14 Aryl radical, C 6 -C 10 Aryl substituted C 6 -C 14 Aryl and
Figure FDA0003710573740000021
wherein R' is H, C 1 -C 4 Alkyl or C 1 -C 4 An alkoxy group; r a 、R b And R c Independently is C 1 -C 4 An alkyl group;
R 3 h, D or trifluoromethanesulfonyl;
R 1 is C 6 -C 14 Aryl radicals, substituted by one or more R 2-1 Substituted C 6 -C 14 Aryl, 5-6 membered heteroaryl with one or more heteroatoms selected from N, O and S, 1-3 heteroatoms, and one or more R 2-2 Substituted 'one or more hetero atoms selected from N, O and S, 5-6 membered heteroaryl with 1-3 hetero atoms', C 1 -C 10 Alkyl or
Figure FDA0003710573740000022
Wherein R' is C 1 -C 4 An alkyl group;
R 2-1 and R 2-2 Independently selected from the following substituents: halogen, C 1 -C 10 Alkyl and C 1 -C 10 An alkoxy group;
R 2 is hydrogen or C 1 -C 4 An alkyl group.
2. The method according to claim 1, wherein the reaction mixture,
when said compound II, except R 3 In addition, X is not R in the ortho-position X Or the ortho position of X forms a ring with the meta position of X, R X Is H,D or trifluoromethanesulfonyl, the reactive sites in compound II are the carbon attached to X and the carbon attached to R 3 Attached carbon, said compound III
Figure FDA0003710573740000023
As a single product;
and/or when the compound II is
Figure FDA0003710573740000024
R 4 In the case of H, D or trifluoromethanesulfonyl, the reactive sites in compound II are "carbon attached to X and" carbon attached to R 3 Attached carbon, and/or, carbon attached to X and carbon attached to R 4 Attached carbon ", said compound III being
Figure FDA0003710573740000031
And/or
Figure FDA0003710573740000032
Wherein the content of the first and second substances,
Figure FDA0003710573740000035
and
Figure FDA0003710573740000036
each independently represents a single bond or a double bond, and the two are not a single bond or a double bond at the same time; ring C is C 6 -C 30 Aromatic ring, by one or more R 3-1 Substituted C 6 -C 30 An aromatic ring, a 5-to 14-membered heteroaromatic ring having one or more heteroatoms selected from N, O and S and 1-3 heteroatoms, or substituted with one or more R 3-2 Substituted "5-14 membered heteroaromatic ring with 1-3 heteroatoms selected from one or more of N, O and S;
R 3-1 and R 3-2 Independently selected from the following substituents: halogen, C 1 -C 10 Alkyl radical, C 1 -C 10 Alkoxy, D, trifluoromethanesulfonyl, halo C 1 -C 4 Alkyl radical, C 1 -C 10 An alkyl-substituted mercapto group,
Figure FDA0003710573740000033
"5-6 membered heteroaryl group containing 1 to 3 hetero atoms selected from N, O and S, one or more hetero atoms 6 -C 14 Aryl radical, C 6 -C 10 Aryl substituted C 6 -C 14 Aryl and
Figure FDA0003710573740000034
wherein R' "is H, C 1 -C 4 Alkyl or C 1 -C 4 An alkoxy group; r d 、R e And R f Independently is C 1 -C 4 An alkyl group.
3. The method according to claim 2,
the ring A is C 6 -C 30 Aromatic ring, by one or more R 1-1 Substituted C 6 -C 30 An aromatic ring, or a 5-14 membered heteroaromatic ring having "N, O or S as heteroatoms and 1";
and/or, in ring A, said R 1-1 Is halogen, C 1 -C 10 Alkyl radical, C 1 -C 10 Alkoxy or halo C1-C4 alkyl;
and/or, said R 1 Is C 6 -C 14 Aryl radicals or by one or more R 2-1 Substituted C 6 -C 14 Aryl radicals, substituted by one or more R 2-2 Substituted 'one or more hetero atoms selected from N, O and S, 5-6 membered heteroaryl with 1-3 hetero atoms', C 1 -C 10 Alkyl or
Figure FDA0003710573740000041
Wherein R' is C 1 -C 4 An alkyl group; said R 2-1 Is halogen or C 1 -C 10 An alkyl group; said R 2-2 Is C 1 -C 10 An alkoxy group;
and/or, the ring B is C 6 -C 30 Aromatic ring, by one or more R 1-1 Substituted C 6 -C 30 An aromatic ring or "5-14 membered heteroaromatic ring with 1-3 heteroatoms selected from one or more of N, O and S";
and/or, X is Br;
and/or when the compound II is
Figure FDA0003710573740000042
The ring C is C 6 -C 30 An aromatic ring or "5-14 membered heteroaromatic ring with 1-3 heteroatoms selected from one or more of N, O and S";
and/or, said R 3 Is H or D;
and/or when the compound II is
Figure FDA0003710573740000043
Said R 4 Is H or D.
4. The method according to claim 3,
the ring A is C 6 -C 30 Aromatic ring, by one or more R 1-1 Substituted C 6 -C 30 An aromatic ring, or a 5-14 membered heteroaromatic ring having "N, O or S as heteroatoms and 1"; in ring A, the R is 1-1 Is halogen, C 1 -C 10 Alkyl radical, C 1 -C 10 Alkoxy or halo C1-C4 alkyl; said R 1 Is C 6 -C 14 Aryl radicals, substituted by one or more R 2-1 Substituted C 6 -C 14 Aryl radicals, substituted by one or more R 2-2 Substituted 'one or more hetero atoms selected from N, O and S, 5-6 membered heteroaryl with 1-3 hetero atoms', C 1 -C 10 Alkyl or
Figure FDA0003710573740000044
Wherein R' is C 1 -C 4 An alkyl group; in ring A, the R is 2-1 Is halogen or C 1 -C 10 An alkyl group; said R 2-2 Is C 1 -C 10 An alkoxy group; the ring B is C 6 -C 30 Aromatic ring, by one or more R 1-1 Substituted C 6 -C 30 Aromatic ring or "5-14 membered heteroaromatic ring with 1-3 heteroatoms selected from one or more of N, O and S", and X is bromine.
5. The method according to claim 2,
when the compound II is
Figure FDA0003710573740000051
R 4 When the group is H, D or trifluoromethanesulfonyl, the ring A is C 6 -C 30 Aromatic ring, by one or more R 1-1 Substituted C 6 -C 30 An aromatic ring, or a 5-14 membered heteroaromatic ring having "N, O or S as heteroatoms and 1"; in ring A, the R is 1-1 Is halogen, C 1 -C 10 Alkyl radical, C 1 -C 10 Alkoxy or halo C1-C4 alkyl; said R 1 Is C 6 -C 14 Aryl radicals, substituted by one or more R 2-1 Substituted C 6 -C 14 Aryl radicals, substituted by one or more R 2-2 Substituted 'one or more hetero atoms selected from N, O and S, 5-6 membered heteroaryl with 1-3 hetero atoms', C 1 -C 10 Alkyl or
Figure FDA0003710573740000052
Wherein R' is C 1 -C 4 An alkyl group; in ring A, the R is 2-1 Is halogen or C 1 -C 10 An alkyl group; said R 2-2 Is C 1 -C 10 An alkoxy group; the ring C is C 6 -C 30 An aromatic ring or "5-14 membered heteroaromatic ring with 1-3 heteroatoms selected from one or more of N, O and S"; x is bromine; said R 4 Is H or D.
6. The method according to claim 4,
ring A is C 6 -C 30 Aromatic ring, by one or more R 1-1 Substituted C 6 -C 30 An aromatic ring, or a 5-14 membered heteroaromatic ring having 1 heteroatom atom "N, O or S", R 1 Is C 6 -C 14 Aryl, or C substituted by one or more halogens 6 -C 14 Aryl radical, C 1 -C 10 Alkyl or
Figure FDA0003710573740000053
R 2 Is hydrogen; ring B is C 6 -C 30 Aromatic rings or substituted by one or more R 1-1 Substituted C 6 -C 30 Aromatic ring, R 1-1 Is D, halogen, C 1 -C 4 Alkyl radical, C 1 -C 10 Alkoxy or halo C1-C4 alkyl, R 3 Is H or D, and X is bromine.
7. The method according to claim 1, wherein the reaction mixture,
when said ring A is C 6 -C 30 When it is an aromatic ring, said C 6 -C 30 The aromatic ring being C 6 -C 14 An aromatic ring;
and/or, when said ring A is substituted by one or more R 1-1 Substituted C 6 -C 30 When it is an aromatic ring, said C 6 -C 30 The aromatic ring being C 6 -C 14 An aromatic ring;
and/or, when said ring A is a "5-14 membered heteroaromatic ring having 1-3 heteroatoms selected from one or more of N, O and S", said "heteroatom selected from one or more of N, O and S", and a "5-14 membered heteroaromatic ring having 1-3 heteroatoms selected from one or more of N, O and S", and a "5-6 membered heteroaromatic ring having 1-3 heteroatoms";
and/or, when said ring A is substituted by one or more R 1-2 Substituted "heteroatoms selected from one or more of N, O and S, heteroWhen the number of atoms is 1-3, the heteroatom is selected from one or more of N, O and S, the 5-14-membered heteroaromatic ring with 1-3 heteroatoms is selected from one or more of N, O and S, and the 5-6-membered heteroaromatic ring with 1-3 heteroatoms;
and/or, when said ring B is C 6 -C 30 When it is an aromatic ring, said C 6 -C 30 The aromatic ring being C 6 -C 14 An aromatic ring;
and/or, when said ring B is substituted by one or more R 1-1 Substituted C 6 -C 30 When it is an aromatic ring, said C 6 -C 30 The aromatic ring being C 6 -C 14 An aromatic ring;
and/or, when said ring B is "5-14 membered heteroaromatic ring with 1-3 heteroatoms selected from one or more of N, O and S", said "heteroatom is selected from one or more of N, O and S", 5-14 membered heteroaromatic ring with 1-3 heteroatoms "is" one or more of N, O and S, 5-6 membered heteroaromatic ring with 1-3 heteroatoms "or" one or more of N, O and S ", 8-10 membered heteroaromatic ring with 1-3 heteroatoms";
and/or, when said ring B is substituted by one or more R 1-2 Substituted ' heteroatom is selected from one or more of N, O and S, 5-14 membered heteroaromatic ring with 1-3 heteroatom ' S, the ' heteroatom is selected from one or more of N, O and S, 5-14 membered heteroaromatic ring with 1-3 heteroatom ' is ' heteroatom is selected from one or more of N, O and S, 5-6 membered heteroaromatic ring with 1-3 heteroatom ' or ' heteroatom is selected from one or more of N, O and S, 8-10 membered heteroaromatic ring with 1-3 heteroatom ' is included ';
and/or, when said R is 1-1 And R 1-2 When independently halogen, said halogen is fluorine, chlorine, bromine or iodine;
and/or, when said R is 1-1 And R 1-2 Independently is C 1 -C 10 When alkyl, said C 1 -C 10 Alkyl is C 1 -C 4 An alkyl group;
and/or whenSaid R 1-1 And R 1-2 Independently is C 1 -C 10 At alkoxy, said C 1 -C 10 Alkoxy is C 1 -C 4 An alkoxy group;
and/or, when said R is 1-1 And R 1-2 Independently is halo C 1 -C 4 When alkyl, said C 1 -C 4 Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl; the halogen is substituted by fluorine, chlorine, bromine or iodine;
and/or, when said R is 1-1 And R 1-2 Independently is C 1 -C 10 When the mercapto group is substituted by an alkyl group, said C 1 -C 10 Alkyl is C 1 -C 4 An alkyl group;
and/or, when said R is a 、R b And R c Independently is C 1 -C 4 When alkyl, said C 1 -C 4 Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;
and/or, when said R' is C 1 -C 4 When alkyl, said C 1 -C 4 Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;
and/or, when said R' is C 1 -C 4 At alkoxy, said C 1 -C 4 Alkoxy is methoxy, ethoxy, n-oxopropyl, iso-oxopropyl, n-butoxy, iso-butoxy or tert-butoxy;
and/or, when said R is 1-1 And R 1-2 Independently represents one or more of heteroatoms selected from N, O and S, and 5-6-membered heteroaryl with 1-3 heteroatoms, wherein the heteroatoms are selected from N, O and S, and the 5-6-membered heteroaryl with 1-3 heteroatoms is the 5-6-membered heteroaryl with N, O or S and 1 heteroatom;
and/or, when said R is 1-1 And R 1-2 Independently is C 6 -C 14 When aryl, said C 6 -C 14 Arylphenyl, naphthyl, anthryl or phenanthryl;
and/or, when said R is 1-1 And R 1-2 Independently is C 6 -C 10 Aryl substituted C 6 -C 14 When aryl, said C 6 -C 10 Aryl is phenyl or naphthyl; said C 6 -C 14 Aryl is phenyl, naphthyl, anthryl or phenanthryl;
and/or, when said R is 1 Is C 6 -C 14 Aryl is said to C 6 -C 14 Aryl is C 6 -C 10 An aryl group;
and/or, when said R is 1 Is represented by one or more R 2-1 Substituted C 6 -C 14 When aryl, said C 6 -C 14 Aryl is C 6 -C 10 An aryl group;
and/or, when said R is 1 When the formula is '5-6-membered heteroaryl with 1-3 heteroatoms selected from one or more of N, O and S', the 'heteroatoms selected from one or more of N, O and S', the '5-6-membered heteroaryl with 1-3 heteroatoms' is '5-6-membered heteroaromatic ring with N, O or S and 1 heteroatom';
and/or, when said R is 1 Is represented by one or more R 2-2 When the substituted heteroatom is one or more of N, O and S and the 5-6-membered heteroaryl with 1-3 heteroatom (S), the heteroatom is one or more of N, O and S, the 5-6-membered heteroaryl with 1-3 heteroatom (S) is the 5-6-membered heteroaryl with N, O or S heteroatom and 1 heteroatom;
and/or, when said R is 1 Is C 1 -C 10 When alkyl, said C 1 -C 10 Alkyl is C 1 -C 4 An alkyl group;
and/or, when said R' is C 1 -C 4 When alkyl, said C 1 -C 4 Alkyl is methyl, ethyl, n-oxy, isopropyl, n-butyl, isobutyl or tert-butyl;
and/or, when said R is 2-1 And R 2-2 When independently halogen, said halogen is fluorine, chlorine, bromine or iodine;
and/or, when said R is 2-1 And R 2-2 Independently is C 1 -C 10 When alkyl, said C 1 -C 10 Alkyl is C 1 -C 4 An alkyl group;
and/or, when said R is 2-1 And R 2-2 Independently is C 1 -C 10 At alkoxy, said C 1 -C 10 Alkoxy is C 1 -C 4 An alkoxy group;
and/or, when said R is 2 Is C 1 -C 4 When alkyl, said C 1 -C 4 Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl.
8. The method according to claim 7,
when said ring A is C 6 -C 30 When it is an aromatic ring, said C 6 -C 30 The aromatic ring is benzene ring, naphthalene ring, anthracene ring or phenanthrene ring;
and/or, when said ring A is substituted by one or more R 1-1 Substituted C 6 -C 30 When it is an aromatic ring, said C 6 -C 30 The aromatic ring is benzene ring, naphthalene ring, anthracene ring or phenanthrene ring;
and/or, when said ring a is a "5-14 membered heteroaromatic ring having 1-3 heteroatoms selected from one or more of N, O and S", said "5-14 membered heteroaromatic ring having 1-3 heteroatoms selected from one or more of N, O and S" 5-6 membered heteroaromatic ring having 1-3 heteroatoms N, O or S "and 1 heteroatom;
and/or, when said ring A is substituted by one or more R 1-2 When the substituted ' heteroatom is selected from one or more of N, O and S, and the number of the heteroatoms is 1-3, and the 5-14-membered heteroaromatic ring ' is adopted, the ' heteroatom is selected from one or more of N, O and S, and the 5-14-membered heteroaromatic ring with the number of the heteroatoms being 1-3 is ' the 5-6-membered heteroaromatic ring with the number of the heteroatoms being N, O or S and the number of the heteroatoms being 1 ';
and/or, when said ring B is C 6 -C 30 When it is an aromatic ring, said C 6 -C 30 The aromatic ring is benzene ring, naphthalene ring, anthracene ring or phenanthrene ring;
and/or, when said ring B is substituted by one or more R 1-1 Substituted C 6 -C 30 When it is an aromatic ring, said C 6 -C 30 The aromatic ring is benzene ring, naphthalene ring, anthracene ring or phenanthrene ring;
and/or, when said ring B is "a 5-14 membered heteroaromatic ring with 1-3 heteroatoms selected from one or more of N, O and S", when the "hetero atom is one or more selected from N, O and S, and the 5-to 14-membered heteroaromatic ring having 1 to 3 hetero atoms" is "hetero atom is one or more selected from N, O and S, and the" hetero atom is 1 to 3, and the "5-to 6-membered heteroaromatic ring" or "hetero atom is one or more selected from N, O and S, and the" hetero atom is 1 to 3, and the "hetero atom is 8 to 10-membered heteroaromatic ring", the 'heteroatom is selected from one or more of N, O and S, the 5-6-membered heteroaromatic ring with 1-3 heteroatom atoms' is 'the 5-6-membered heteroaromatic ring with N, O heteroatom or S heteroatom and 1 heteroatom atom'; the heteroatom is selected from one or more of N, O and S, the 8-10-membered heteroaromatic ring with 1-3 heteroatoms is ' 8-10-membered heteroaromatic ring with N, O or S and 1 heteroatom, the ' 8-10-membered heteroaromatic ring with N, O or S and 2 heteroatoms ', or ' 8-10-membered heteroaromatic ring with N, O and S and 2 heteroatoms ';
and/or, when said ring B is substituted by one or more R 1-2 Substituted ' heteroatom is selected from one or more of N, O and S, 5-14 membered heteroaromatic ring with 1-3 heteroatom ' S, the ' heteroatom is selected from one or more of N, O and S, 5-14 membered heteroaromatic ring with 1-3 heteroatom ' is ' heteroatom is selected from one or more of N, O and S, 5-6 membered heteroaromatic ring with 1-3 heteroatom ' or ' heteroatom is selected from one or more of N, O and S, 8-10 membered heteroaromatic ring with 1-3 heteroatom ' is included '; the heteroatom is selected from one or more of N, O and S, the 5-6-membered heteroaromatic ring with 1-3 heteroatom (S) is the 5-6-membered heteroaromatic ring with N, O heteroatom or S heteroatom and 1 heteroatomA ring "; the heteroatom is selected from one or more of N, O and S, the 8-10-membered heteroaromatic ring with 1-3 heteroatoms is ' 8-10-membered heteroaromatic ring with N, O or S and 1 heteroatom, the ' 8-10-membered heteroaromatic ring with N, O or S and 2 heteroatoms ', or ' 8-10-membered heteroaromatic ring with N, O and S and 2 heteroatoms ';
and/or, when said R is 1-1 And R 1-2 Independently is halo C 1 -C 4 When alkyl, said halo C 1 -C 4 Alkyl being halogeno C 1 -C 2 An alkyl group;
and/or, when said R is 1-1 And R 1-2 When the "5-6 membered heteroaryl group with 1-3 hetero atoms selected from one or more of N, O and S" is independently used, the "hetero atoms selected from one or more of N, O and S" and the 5-6 membered heteroaryl group with 1-3 hetero atoms is pyridyl;
and/or, when said R is 1 Is C 6 -C 14 Aryl is said to C 6 -C 14 Aryl is phenyl or naphthyl;
and/or, when said R is 1 Is represented by one or more R 2-1 Substituted C 6 -C 14 When aryl, said C 6 -C 14 Aryl is phenyl or naphthyl;
and/or, when said R is 1 When the "5-6 membered heteroaryl group with 1-3 heteroatoms selected from one or more of N, O and S" is used, the "one or more of N, O and S" is used, and the 5-6 membered heteroaryl group with 1-3 heteroatoms "is pyridyl.
9. The method according to claim 8,
when the ring A is a 5-14 membered heteroaromatic ring with 1-3 heteroatoms selected from one or more of N, O and S, the "heteroatom is one or more of N, O and S, and the 5-14 membered heteroaromatic ring with 1-3 heteroatoms" is a pyridine ring;
and/or, when the ring B is "one or more hetero atoms selected from N, O and S, 5-14 membered heteroaromatic ring having 1-3 hetero atoms", the "hetero atom is selected from N, O and S, 5-14 membered heteroaromatic ring having 1-3 hetero atoms" is "one or more hetero atoms selected from N, O and S, 5-6 membered heteroaromatic ring having 1-3 hetero atoms", "hetero atom is N, O or S, and 8-10 membered heteroaromatic ring having 1 hetero atom", "hetero atom is N, O or S, and 8-10 membered heteroaromatic ring having 2 hetero atoms" or "8-10 membered heteroaromatic ring containing N, O and S and 2 hetero atoms", the "hetero atom is selected from N, O and S, the 5-6 membered heteroaromatic ring with 1-3 heteroatoms is a thiophene ring or a pyridine ring; the 8-10 membered heteroaromatic ring with 1 heteroatom atom is N, O or S, and is a quinoline ring, an isoquinoline ring, a benzofuran ring or a benzothiophene ring; the "8-to 10-membered heteroaromatic ring having N, O or S as a heteroatom and 2 heteroatoms" is a quinoxaline ring; the 8-10 membered heteroaromatic ring containing N, O heteroatoms and 2 heteroatoms is a benzothiazole ring;
and/or, when said R is 1-1 And R 1-2 Independently is halo C 1 -C 4 When alkyl, said halo C 1 -C 4 Alkyl being fluoro C 1 -C 2 An alkyl group.
10. The method according to claim 9,
when said R is 1-1 And R 1-2 Independently is halo C 1 -C 4 When alkyl, said halo C 1 -C 4 The alkyl group is trifluoromethyl.
11. The method according to claim 2,
when said ring C is C 6 -C 30 When it is an aromatic ring, said C 6 -C 30 The aromatic ring being C 6 -C 14 An aromatic ring;
and/or, when said ring C is substituted by one or more R 3-1 Substituted C 6 -C 30 When it is an aromatic ring, said C 6 -C 30 The aromatic ring being C 6 -C 14 An aromatic ring;
and/or, when said ring C is "5-14 membered heteroaromatic ring with 1-3 heteroatoms selected from one or more of N, O and S", said "heteroatom selected from one or more of N, O and S", 5-14 membered heteroaromatic ring with 1-3 heteroatoms "is" one or more of N, O and S, 5-6 membered heteroaromatic ring with 1-3 heteroatoms "or" one or more of N, O and S ", 8-10 membered heteroaromatic ring with 1-3 heteroatoms";
and/or, when said ring C is substituted by one or more R 3-2 Substituted ' heteroatom is selected from one or more of N, O and S, 5-14 membered heteroaromatic ring with 1-3 heteroatom ' S, the ' heteroatom is selected from one or more of N, O and S, 5-14 membered heteroaromatic ring with 1-3 heteroatom ' is ' heteroatom is selected from one or more of N, O and S, 5-6 membered heteroaromatic ring with 1-3 heteroatom ' or ' heteroatom is selected from one or more of N, O and S, 8-10 membered heteroaromatic ring with 1-3 heteroatom ' is included ';
and/or, when said R is 3-1 And R 3-2 When independently halogen, said halogen is fluorine, chlorine, bromine or iodine;
and/or, when said R is 3-1 And R 3-2 Independently is C 1 -C 10 When alkyl, said C 1 -C 10 Alkyl is C 1 -C 4 An alkyl group;
and/or, when said R is 3-1 And R 3-2 Independently is C 1 -C 10 At alkoxy, said C 1 -C 10 Alkoxy is C 1 -C 4 An alkoxy group;
and/or, when said R is 3-1 And R 3-2 Independently is halo C 1 -C 4 When alkyl, said C 1 -C 4 Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl; the halogen is substituted by fluorine, chlorine, bromine or iodine;
and/or, when said R is 3-1 And R 3-2 Independently is C 1 -C 10 When the mercapto group is substituted by an alkyl group, said C 1 -C 10 Alkyl is C 1 -C 4 An alkyl group;
and/or, when said R is d 、R e And R f Independently is C 1 -C 4 When alkyl, said C 1 -C 4 Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;
and/or, when R' is C 1 -C 4 When alkyl, said C 1 -C 4 Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;
and/or, when R' is C 1 -C 4 At alkoxy, said C 1 -C 4 Alkoxy is methoxy, ethoxy, n-oxopropyl, iso-oxopropyl, n-butoxy, iso-butoxy or tert-butoxy;
and/or, when said R is 3-1 And R 3-2 Independently represents one or more of heteroatoms selected from N, O and S, and 5-6-membered heteroaryl with 1-3 heteroatoms, wherein the heteroatoms are selected from N, O and S, and the 5-6-membered heteroaryl with 1-3 heteroatoms is the 5-6-membered heteroaryl with N, O or S and 1 heteroatom;
and/or, when said R is 3-1 And R 3-2 Independently is C 6 -C 14 When aryl, said C 6 -C 14 Aryl is phenyl, naphthyl, anthryl or phenanthryl;
and/or, when said R is 3-1 And R 3-2 Independently is C 6 -C 10 Aryl substituted C 6 -C 14 When aryl, said C 6 -C 10 Aryl is phenyl or naphthyl; said C 6 -C 14 Aryl is phenyl, naphthyl, anthryl or phenanthryl.
12. The method according to claim 11,
when the ring C is "one or more heteroatoms selected from N, O and S, 5-to 14-membered heteroaromatic ring (S) having 1 to 3 heteroatoms", the "one or more heteroatoms selected from N, O and S, 5-to 14-membered heteroaromatic ring (S) having 1 to 3 heteroatoms" is "one or more heteroatoms selected from N, O and S, 5-to 6-membered heteroaromatic ring (S) having 1 to 3 heteroatoms" or "one or more heteroatoms selected from N, O and S, 8-to 10-membered heteroaromatic ring (S) having 1 to 3 heteroatoms", the "one or more heteroatoms selected from N, O and S, 5-to 6-membered heteroaromatic ring (S) having 1 to 3 heteroatoms" is "5-to 6-membered heteroaromatic ring (S) having N, O or S as heteroatoms, and 5-to 6-membered heteroaromatic ring (S) having 1 atom as heteroatoms"; the heteroatom is selected from one or more of N, O and S, the 8-10-membered heteroaromatic ring with 1-3 heteroatoms is ' 8-10-membered heteroaromatic ring with N, O or S and 1 heteroatom, the ' 8-10-membered heteroaromatic ring with N, O or S and 2 heteroatoms ', or ' 8-10-membered heteroaromatic ring with N, O and S and 2 heteroatoms ';
and/or, when said ring C is substituted by one or more R 3-2 When the substituted ' heteroatom is selected from one or more of N, O and S, and the 5-14-membered heteroaromatic ring with 1-3 heteroatoms ' is adopted, the ' heteroatom is selected from one or more of N, O and S, and the ' 5-6-membered heteroaromatic ring with 1-3 heteroatoms ' is ' 5-6-membered heteroaromatic ring with N, O or S heteroatoms and 1 heteroatom is adopted '; the heteroatom is selected from one or more of N, O and S, the 8-10-membered heteroaromatic ring with 1-3 heteroatoms is ' 8-10-membered heteroaromatic ring with N, O or S and 1 heteroatom, the ' 8-10-membered heteroaromatic ring with N, O or S and 2 heteroatoms ', or ' 8-10-membered heteroaromatic ring with N, O and S and 2 heteroatoms ';
and/or, when said R is 3-1 And R 3-2 Independently is halo C 1 -C 4 When alkyl, said halo C 1 -C 4 Alkyl being halogeno C 1 -C 2 An alkyl group;
and/or, when said R is 3-1 And R 3-2 And when the heteroatom is one or more of N, O and S and the 5-6 membered heteroaryl with 1-3 heteroatoms independently, the heteroatom is one or more of N, O and S and the 5-6 membered heteroaryl with 1-3 heteroatoms is pyridyl.
13. The method according to claim 12,
when the ring C is "one or more of hetero atom selected from N, O and S, 5-14 membered hetero aromatic ring having 1-3 hetero atoms", the "hetero atom selected from one or more of N, O and S, 5-14 membered hetero aromatic ring having 1-3 hetero atoms" is "one or more of hetero atom selected from N, O and S, 5-6 membered hetero aromatic ring having 1-3 hetero atoms", "hetero atom is N, O or S, 8-10 membered hetero aromatic ring having 1 hetero atom", "hetero atom is N, O or S, and 8-10 membered hetero aromatic ring having 2 hetero atoms" or "8-10 membered hetero aromatic ring having two hetero atoms of N, O and S and 2 hetero atoms", the "hetero atom selected from one or more of N, O and S, the 5-6 membered heteroaromatic ring with 1-3 heteroatoms is a thiophene ring or a pyridine ring; the 8-10 membered heteroaromatic ring with 1 heteroatom atom is N, O or S, and is a quinoline ring, an isoquinoline ring, a benzofuran ring or a benzothiophene ring; the "8-to 10-membered heteroaromatic ring having N, O or S as a heteroatom and 2 heteroatoms" is a quinoxaline ring; the 8-10 membered heteroaromatic ring containing N, O heteroatoms and 2 heteroatoms is a benzothiazole ring;
and/or, when said R is 3-1 And R 3-2 Independently is halo C 1 -C 4 When alkyl, said halo C 1 -C 4 Alkyl being fluoro C 1 -C 2 An alkyl group.
14. The method according to claim 13, wherein,
when said R is 3-1 And R 3-2 Independently is halo C 1 -C 4 When alkyl, said halo C 1 -C 4 The alkyl group is trifluoromethyl.
15. The method according to claim 2,
in ring C, when with R 3 Of the carbon bound to R 4 Steric hindrance is preferably considered when the steric hindrance and the acidity of the connected carbon are different; when with R 3 The carbon attached being more sterically hindered than R 4 Steric hindrance of the carbon to which it is attached, preferably with R 4 The attached carbons react and vice versa;
and/or, in ring C, when with R 3 Of the carbon bound to R 4 Steric hindrance of the attached carbon, corresponding to R 3 The carbon to which it is attached is more acidic than R 4 Acidity of the carbon to which it is attached, preferably with R 3 The attached carbons react and vice versa;
and/or, in ring C, when R is 3 Compared with R 4 When it is a readily removable substituent group, with R 3 The attached carbons react and vice versa; the leaving priority of the easy-leaving substituent group is OTf > D > H.
16. The process according to claim 1 or 2, wherein compound I is of any one of the following structures;
Figure FDA0003710573740000151
and/or, the compound II is any one of the following structures:
Figure FDA0003710573740000161
17. the production method according to claim 1 or 2,
the solvent is an ether solvent;
and/or the volume mol ratio of the solvent to the compound I is 1-10L/mol;
and/or the molar ratio of the palladium acetate to the compound I is 0.01-0.10;
and/or the ligand is
Figure FDA0003710573740000162
And/or the molar ratio of the ligand to the compound I is 0.05-0.4;
and/or the acetate of the alkali metal is one or more of potassium acetate, sodium acetate and cesium acetate; the carbonate of the alkali metal is one or more of potassium carbonate, sodium carbonate and cesium carbonate; the PivO acid salt of the alkali metal is one or more of PivO potassium, PivO sodium and PivO cesium;
and/or the molar ratio of the alkali to the compound I is 0.5-4;
and/or the molar ratio of the compound II to the compound I is 1-4;
and/or the reaction temperature of the reaction is 90-170 ℃;
and/or, the reaction is carried out under anhydrous conditions.
18. The method of claim 17,
the ether solvent is 1, 4-dioxane;
and/or the volume mol ratio of the solvent to the compound I is 3-8L/mol;
and/or the molar ratio of the palladium acetate to the compound I is 0.03-0.06;
and/or the molar ratio of the ligand to the compound I is 0.1-0.3;
and/or the molar ratio of the alkali to the compound I is 1-3;
and/or the molar ratio of the compound II to the compound I is 1-2;
and/or the reaction temperature of the reaction is 110-160 ℃.
19. The method of claim 17, wherein the method comprisesThe solvent is an ether solvent; the volume mol ratio of the solvent to the compound I is 3-8L/mol; the molar ratio of the palladium acetate to the compound I is 0.03-0.06; the ligand is
Figure FDA0003710573740000171
The molar ratio of the ligand to the compound I is 0.1-0.3; the alkali is one or more of acetate of alkali metal, carbonate of alkali metal and PivO acid salt of alkali metal; the molar ratio of the alkali to the compound I is 1-3; the molar ratio of the compound II to the compound I is 1-2; the reaction temperature is 110-160 ℃; the reaction is carried out under anhydrous conditions.
20. The method of claim 19, wherein the acetate salt of an alkali metal is one or more of potassium acetate, sodium acetate, and cesium acetate; the carbonate of the alkali metal is one or more of potassium carbonate, sodium carbonate and cesium carbonate; the PivO acid salt of the alkali metal is one or more of PivO potassium, PivO sodium and PivO cesium.
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