CN117886659A - Method for preparing olefin by iridium-catalyzed alkane transfer dehydrogenation, ligand and complex - Google Patents

Method for preparing olefin by iridium-catalyzed alkane transfer dehydrogenation, ligand and complex Download PDF

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CN117886659A
CN117886659A CN202410043645.7A CN202410043645A CN117886659A CN 117886659 A CN117886659 A CN 117886659A CN 202410043645 A CN202410043645 A CN 202410043645A CN 117886659 A CN117886659 A CN 117886659A
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formula
alkyl
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吴雨恒
黄正
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Shanghai Institute of Organic Chemistry of CAS
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Shanghai Institute of Organic Chemistry of CAS
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Abstract

The invention discloses a method for preparing olefin by iridium-catalyzed alkane transfer dehydrogenation, a ligand and a complex, and provides a method for preparing olefin by iridium-catalyzed alkane transfer dehydrogenation, which comprises the following steps of carrying out dehydrogenation reaction on a compound containing a fragment shown as a formula II-1 in the presence of a catalyst and the compound shown as a formula I; the compound shown in the formula III-1 is obtained. The method has better transfer dehydrogenation effect on alkane with larger steric hindrance, and the corresponding alkene compound is prepared by iridium catalysis in the presence of the ligand, so that the synthesis efficiency is high.

Description

Method for preparing olefin by iridium-catalyzed alkane transfer dehydrogenation, ligand and complex
Technical Field
The invention relates to the technical field of transition metal catalyzed transfer dehydrogenation, in particular to a method for preparing olefin by iridium catalyzed alkane transfer dehydrogenation, a ligand and a complex.
Background
Olefins are the most important functional groups in organic chemistry, and the preparation of olefins by alkane dehydrogenation is of great importance. Felkin and the Crabtree problem group report earlier that the catalytic efficiency of the phosphine ligand catalyzed alkane dehydrogenation is lower, most of which are equivalent reactions or require higher catalyst usage (See a)Crabtree,R.H.;Mihelcic,J.M.;Quirk,J.M.Journal of the American Chemical Society 1979,101,7738-7740;b)Baudry,D.;Ephritikhine,M.;Felkin,H.Journal of the Chemical Society,Chemical Communications 1980,1243-1244).
Jensen, brookhart, goldman, huang et al subsequently reported a pincer ligand coordinated catalytic system, which had better catalytic activity for dehydrogenation of linear alkanes and cycloalkanes due to better thermal stability. However, due to the structural rigidity, the catalyst has larger steric hindrance and has poor alkane dehydrogenation effect on large steric hindrance (See a)Kumar,A.;Bhatti,T.M.;Goldman,A.S.Chemical Reviews 2017,117,12357-12384b)Tang,X.;Jia,X.;Huang,Z.Chemical Science 2018,9,288-299).
In addition, the poor compatibility of the functional groups ,(See a)Dinh,L.V.;Li,B.;Kumar,A.;Schinski,W.;Field,K.D.;Kuperman,A.;Celik,F.E.;Goldman,A.S.ACS Catalysis 2016,6,2836-2841;b)Tang,X.;Jia,X.;Huang,Z.Journal of the American Chemical Society 2018,140,4157-4163), of the catalytic system is difficult to apply to complex molecular synthesis or post-modification.
The hydrocarbon bond of the substituted alkane sp 3 with large steric hindrance widely exists in various drug molecules and natural products, and if the dehydrogenation reaction can be carried out on the substituted alkane in complex molecules, the post-modification and synthesis efficiency of the drug molecules and the natural products can be greatly improved, and the post-modification and synthesis method of the drug molecules and the natural products can be widened.
Currently, few reports on dehydrogenation of large-steric-hindrance alkanes (1, 1-disubstituted alkanes, 1-DSE or 1, 2-disubstituted alkanes, 1, 2-DSE) have been made, and the existing reports mainly focus on alkane dehydrogenation reactions containing a directing group:
In 2008, the Yu group reported that benzoquinone was used as an oxidant in palladium-catalyzed dehydrogenation of substituted alkanes under conditions of amino oxazoline orientation, such substrates were highly limited (Giri, r.; maugel, n.; foxman, b.m.; yu, j. —q. Organometallics 2008,27,1667-1670).
In 2012, the Baran group reported that the dehydrogenation reaction of a radical process using Tz ° as a director, the reaction was subjected to two radical process oxidations to obtain the corresponding olefin compound. The director groups are present to generate free radicals and to control the 1, n-hydrogen migration process to produce product olefins. With the end of the reaction, the director groups were also eliminated (Voica, A.F.; mendoza, A.; gutekunst, W.R.; fraga, J.O.; baran, P.S.Nat Chem 2012,4,629-635.).
In 2017 Gevorgyan, it was reported that the dehydrogenation reaction was completed by carbon-iodine bond homolytic cleavage-initiated radical-radical transfer-metal-participated reductive elimination using palladium-catalyzed alcohol-directed dehydrogenation reaction under light (Parasram, m.; chuentragool, p.; wang, y.; shi, y.; gevorgyan, v.j.am.chem.soc.2017,139, 14857-14860.).
In 2021, the group of studio topics developed a similar strategy to accomplish the dehydrogenation of guided substituted alkanes, the authors used copper as a catalyst and the dehydrogenation was also accomplished by means of a strategy of free radical migration, which gave the corresponding alkene product in moderate yields (Xia, y.; jana, k.; studio, a.chem. Eur. J.2021,27, 16621-16625).
The Huang Zheng group developed a transfer dehydrogenation reaction of 1, 1-disubstituted alkanes using the biphosphine ligand DTBM-SEGPHOS with iridium (Wang, k.; gan, l.; wu, y.; zhou, m.; j.; liu, g.; huang, z.
Disclosure of Invention
The invention aims to overcome the defects that in the prior art, dehydrogenation reports on large-steric-hindrance alkane (1, 1-disubstituted alkane, 1-DSE or 1, 2-disubstituted alkane, 1, 2-DSE) are few and the existing reports mainly focus on alkane dehydrogenation reactions containing guide groups. The invention provides a method for preparing olefin by iridium-catalyzed alkane transfer dehydrogenation, a ligand and a complex, which have better transfer dehydrogenation effect on alkane with larger steric hindrance, and the method for preparing corresponding olefin compounds by iridium catalysis in the presence of the ligand has higher catalytic conversion efficiency.
The aim of the invention is realized by the following technical scheme:
The invention provides a preparation method of an olefin compound, which comprises the following steps: carrying out dehydrogenation reaction on a compound containing a fragment shown in a formula II-1 in the presence of a catalyst and a compound shown in a formula I to obtain a compound containing a fragment shown in a formula III-1;
R 10 and R 11 are independently C 1-C10 alkyl optionally substituted with 1,2 or 3R 10-1, C 6-C20 aryl optionally substituted with 1,2 or 3R 10-2, C 1-C10 alkoxy optionally substituted with 1,2 or 3R 10-3, 1,2 or 3 heteroatoms optionally substituted with 1,2 or 3R 10-4 are independently selected from N, O and S, 1,2 or 3 5-9 membered heteroaryl having 1,2 or 3 heteroatoms, cycloalkyl of C 6-C12 optionally substituted with 1,2 or 3R 10-5 or 3 heteroatoms optionally substituted with 1,2 or 3R 10-6 are independently selected from N, O and S, 1,2 or 3, 3-6 membered heterocycloalkyl having 1,2 or 3 heteroatoms;
R 10-1、R10-2、R10-3、R10-4、R10-5 or R 10-6 are independently C 1-C6 alkyl or C 1-C6 alkoxy;
Wherein,
The compound shown as the formula I has the following structure:
R 1 is H, C 1-C10 alkyl optionally substituted with 1, 2 or 3R 1-1;
r 1-1 is C 1-C6 alkyl;
The catalyst comprises a metal complex formed by a compound shown as a formula IV-1 or IV-2 and iridium, and/or a mixture of the compound shown as the formula IV-1 or IV-2 and iridium;
r 2、R3、R4、R5、R6、R7、R8 and R 9 are independently H, C 1-C6 alkyl, C 1-C6 alkoxy or halogen;
R 12、R13、R18 and R 19 are independently H, C 1-C6 alkyl, C 1-C6 alkoxy or halogen;
Or R 14、R15 taken together with the atoms to which they are attached form a C 6-C10 aryl group, a C 6-C10 aryl group substituted with 1,2 or 3R A-1, a "6-12 membered heterocycloalkyl group having 1,2 or 3 heteroatoms" selected from N, O and S, or a "6-12 membered heterocycloalkyl group having 1,2 or 3 heteroatoms" substituted with 1,2 or 3R A-2, a "heteroatom selected from 1,2 or 3 heteroatoms" selected from N, O and S, a 6-12 membered heterocycloalkyl group having 1,2 or 3 heteroatoms;
Or R 16、R17 taken together with the atoms to which they are attached form a C 6-C10 aryl group, a C 6-C10 aryl group substituted with 1,2 or 3R A-1, a "6-12 membered heterocycloalkyl group having 1,2 or 3 heteroatoms" selected from N, O and S, or a "6-12 membered heterocycloalkyl group having 1,2 or 3 heteroatoms" substituted with 1,2 or 3R A-2, a "heteroatom selected from 1,2 or 3 heteroatoms" selected from N, O and S, a 6-12 membered heterocycloalkyl group having 1,2 or 3 heteroatoms;
Or R 15、R16 taken together with the atoms to which they are attached form a "heteroatom is O, a 7-13 membered heterocyclic ring having 2 heteroatoms" or a "heteroatom substituted with 1 or 2R A-3 is O, a 7-13 membered heterocyclic ring having 2 heteroatoms";
r A-1 and R A-2 are independently C 1-C6 alkyl or C 1-C6 alkoxy or halogen;
ar 1 and Ar 2 are independently C 6-C10 aryl or C 6-C10 aryl substituted with 1-5R B-1;
R B-1 is independently C 1-C6 alkyl, C 1-C6 alkoxy or
R B-1-1、RB-1-2 and R B-1-3 are independently C 1-C6 alkyl;
Ar 3 and Ar 4 are independently C 6-C10 aryl or C 6-C10 aryl substituted with 1-5R B-2;
R B-2 is independently C 1-C6 alkyl, C 1-C6 alkoxy or
R B-1-1、RB-1-2 and R B-1-3 are independently C 1-C6 alkyl.
In a preferred embodiment, certain groups in the compounds of formula II-1, formula III-1, formula I and formula IV are defined as follows, and other groups are defined as described in any of the other embodiments (hereinafter referred to as "in a particular embodiment").
In one embodiment, in R 1, the C 1-C10 alkyl is C 1-C6 alkyl, preferably ethyl.
In one embodiment, in R 1-1, the C 1-C6 alkyl is C 1-C4 alkyl, preferably methyl.
In one embodiment, in R 5 and R 6, the C 1-C6 alkoxy group is methoxy.
In one embodiment, in Ar 1 and Ar 2, the C 6-C10 aryl is phenyl.
In one embodiment, in R B-1, the C 1-C6 alkoxy group is methoxy.
In one embodiment, in R B-1-1、RB-1-2 and R B-1-3, the C 1-C6 alkyl is independently methyl or isopropyl.
In one embodiment, in R 10 and R 11, the C 1-C10 alkyl groups are independently C 1-C6 alkyl groups, preferably independently methyl, ethyl or n-hexyl.
In one embodiment, in R 10 and R 11, the cycloalkyl groups of C 6-C12 are independently 1-4 ring cycloalkanes, preferably 4 rings, more preferably adamantane.
In one embodiment, in R 10 and R 11, the C 6-20 aryl is independently C 6-10 aryl, preferably phenyl.
In one embodiment, in R 10-1, the C 1-C6 alkyl is methyl.
In one embodiment, R 14、R15、R16 and R 17 are the same, the "heteroatom is selected from 1,2 or 3 of N, O and S, and the" medium "heteroatom of 3-12 membered heterocycloalkyl having 1,2 or 3 heteroatoms is selected from O.
In one embodiment, R 14、R15、R16 and R 17 are the same, and the "heteroatom is 1,2 or 3 of N, O and S, and the number of heteroatoms is 2 in the 3-12 membered heterocycloalkyl group having 1,2 or 3 heteroatoms".
In one embodiment, R 14、R15、R16 and R 17 are the same, the "heteroatom is 1,2 or 3 of N, O and S, and the 6-12 membered heterocycloalkyl in the 6-12 membered heterocycloalkyl having 1,2 or 3 heteroatoms" is a 6 membered heterocycloalkyl.
In one embodiment, in Ar 3 and Ar 4, the C 6-C10 aryl is phenyl.
In one embodiment, the compound containing the fragment of II-1 is a compound of II-1.
In one embodiment, R 10 and R 11 are independently C 1-C10 alkyl optionally substituted with 1,2, or 3R 10-1, unsubstituted C 6-C20 aryl, or unsubstituted C 6-C12 cycloalkyl; preferably C 1-C10 alkyl optionally substituted with 1,2 or 3R 10-1 or unsubstituted C 6-C12 cycloalkyl.
In one embodiment, R 1 is C 1-C10 alkyl optionally substituted with 2R 1-1.
In one embodiment, R 2、R3、R4、R7、R8、R9、R12、R13、R18 or R 19 are independently H.
In one embodiment, R 5 and R 6 are independently C 1-C6 alkoxy.
In one embodiment, ar 1 and Ar 2 are independently C 6-C10 aryl substituted with 2 or 3R B-1.
In one embodiment, R B-1 is independently C 1-C6 alkoxy or
In one embodiment, R 14、R15, together with the atoms to which they are attached, forms a "6-12 membered heterocycloalkyl having 1, 2 or 3 heteroatoms selected from 1, 2 or 3 of N, O and S".
In one embodiment, R 16、R17, together with the atoms to which they are attached, forms a "6-12 membered heterocycloalkyl having 1, 2 or 3 heteroatoms selected from 1, 2 or 3 of N, O and S".
In one embodiment, ar 3 and Ar 4 are independently C 6-C10 aryl substituted with 2R B-2.
In one embodiment, R B-2 is independently
In one embodiment, the compound containing the fragment of formula II-1 is any one of the following:
in one embodiment, the compound containing the fragment of formula III-1 is any one of the following:
In one embodiment, the compound of formula I is
In one embodiment, the metal complex is:
Wherein ,R2、R3、R4、R5、R6、R7、R8、R9、R12、R13、R14、R15、R16、R17、R18、R19、Ar1、Ar2、Ar3 and Ar 4 are as described in any one of the present inventions;
Preferably wherein Ar 3 and Ar 4 in formula A-1 are/>
In one embodiment, the compound of formula IV-1 is
In one embodiment, the compound of formula IV-2 is
In one embodiment, the molar ratio of the compound of formula IV-1 or IV-2 to the compound of formula I is (0.0005-0.1): 1; preferably (0.0005-0.05): 1; also preferred is 0.0005: 1. 0.0033:1. 0.1:1 or 0.02:1, more preferably 0.0005:1 or 0.0033:1, particularly preferably 0.0033:1.
In one embodiment, the iridium is Ir +, preferably [ Ir (cod) Cl ] 2,[Ir(coe)2Cl]2 or [ Ir (C 2H4)2Cl]2), such as [ Ir (cod) Cl ] 2.
In one embodiment, the molar ratio of iridium to the compound shown in formula I is (0.00025-0.05): 1; preferably 0.00025:1, 0.05:1, 0.01:1 or 0.0017:1, still preferably 0.00025:1 or 0.0017:1, more preferably 0.0017:1.
In one embodiment, the molar ratio of the compound containing the fragment of formula II-1 to the compound of formula I is (1-10): 1, preferably 5:1, 3.3:1 or 1:1, still preferably 5:1 or 3.3:1, more preferably 3.3:1.
In one embodiment, the alkane transfer dehydrogenation reaction may be carried out in the presence or absence of a solvent, and when in the presence of a solvent, the solvent is a benzene-based solvent, such as one or more selected from toluene, xylene, and trimethylbenzene, such as toluene.
In one embodiment, the temperature of the alkane transfer dehydrogenation reaction is from 100 ℃ to 200 ℃, preferably from 150 ℃ to 200 ℃, for example 150 ℃.
In a certain scheme, the alkane transfer dehydrogenation reaction time is 1min-24h; preferably 4h-18h, for example 4h or 18h.
In one embodiment, the alkane transfer dehydrogenation reaction further comprises a post-treatment step, followed by cooling and sampling gas chromatographic detection.
In one embodiment, the reaction mass of the alkane transfer dehydrogenation reaction consists of: the compound shown in the formula I, the compound shown in the formula II-1 and the catalyst.
The invention provides a compound shown as a formula IV-1,
R 2、R3、R4、R5、R6、R7、R8、R9、Ar1 and Ar 2 are as defined in any one of the present inventions;
And the formula IV-1 satisfies the following conditions: when Ar 1 and Ar 2 are simultaneously substituted with two R B-1, R B-1 are not simultaneously
Preferably, the compound shown in the formula IV-1 is
The present invention provides a complex wherein ,R2、R3、R4、R5、R6、R7、R8、R9、R12、R13、R14、R15、R16、R17、R18、R19、Ar1、Ar2、Ar3 and Ar 4 are as described in any one of the present invention.
In one embodiment, the complex is of any structure,
Wherein Ar 3 and Ar 4 in formula A-1 are/>
The invention also provides the use of a complex as described above in a dehydrogenation reaction according to any one of the invention.
In the present invention, the metal complex formed by the compound of formula IV-1 or IV-2 and iridium and the mixture of the compound of formula IV-1 or IV-2 and iridium have the same or similar effects.
Unless otherwise indicated, the terms used in the present invention have the following meanings:
The term "alkyl" refers to a straight or branched chain alkyl group having the indicated number of carbon atoms (e.g., C 1～C10、C1～C6). Alkyl groups include, but are not limited to, methyl, ethyl, t-butyl, n-hexyl, and the like.
The term "alkoxy" refers to the group R X -O-, wherein R X is alkyl as defined above.
The term "cycloalkyl" refers to a saturated, monocyclic or polycyclic group consisting of only carbon atoms having the indicated number of carbon atoms (e.g., C 6～C12). Polycyclic alkanes include, but are not limited to adamantane and the like.
The term "aryl" refers to a cyclic group consisting of only carbon atoms, having the indicated number of carbon atoms (e.g., C 6～C20), which is monocyclic or polycyclic, and at least one ring is aromatic (in accordance with the shock rule). Aryl groups are linked to other fragments in the molecule through aromatic or non-aromatic rings. Aryl groups include, but are not limited to, phenyl, and the like.
The term "halogen" refers to fluorine, chlorine, bromine or iodine.
The term "heterocycloalkyl" refers to a cyclic group of a specified number of ring atoms (e.g., 6-12 membered), of a specified number of heteroatoms (e.g., 1, 2, or 3), of a specified heteroatom species (one or more of N, O and S), which is a single ring, bridged ring, or spiro ring, and each ring is saturated. Bridged ring means a polycyclic ring having two or more atoms in common between the monocyclic rings. Spiro refers to polycyclic rings that share one atom between the rings. Heterocycloalkyl groups include, but are not limited to, azetidinyl, tetrahydropyrrolyl, tetrahydrofuranyl, morpholinyl, piperidinyl, 1, 3-dioxan, 1, 4-dioxan, and the like.
The above preferred conditions can be arbitrarily combined on the basis of not deviating from the common knowledge in the art, and thus, each preferred embodiment of the present invention can be obtained.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that: the invention provides a method, a ligand and a complex for preparing olefin by iridium-catalyzed alkane transfer dehydrogenation, which can be used for dehydrogenating various products including complex molecules by using common olefin as a hydrogen acceptor, and the generated olefin functional group has strong conversion potential and provides a great deal of possibility and opportunities for post-modification of drug molecules.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
The general operation of iridium-catalysed selective alkane transfer dehydrogenation reactions is: the P-phos ligand and iridium source were weighed in an argon filled glove box (water content <0.01ppm oxygen content <0.01 ppm). The above mixture was dissolved in a solvent, stirred at room temperature for two hours, and then a dehydrogenation feed and a hydrogen acceptor were added to the above reaction system and heated at 150℃for several times. After the reaction was completed, the product was detected by GC.
Example 1: synthesis of 4a
Step 1: 4-OMe-3,5-TMS Synthesis of MeO-BIPHEP-Oxide (6 a): the dried three-necked flask was connected to a spherical condenser, argon was purged 5 times through a double tube, cooled to room temperature, and 5 (243.2 mg,0.5 mmol) and NaI (374.7 mg,2.5 mmol) were added to the three-necked flask to again purge argon 5 times. To the flask was then added 20mL of anhydrous CH 3 CN and TMSCl (271.6 mg,2.5 mmol) and the resulting yellow cloudy solution was reacted in an oil bath at 50℃for 2 hours. After completion of the reaction, 10mL of anhydrous DCM and 0.1mL of DMF were added to the mixture, and oxalyl chloride (0.8 mL,10.0 mmol) was slowly added dropwise in an oil bath at 40℃and the reaction was continued for 2 hours, whereupon the solution turned red. After 2h, all solvents and oxalyl chloride were drained to give the phosphonochloride intermediate, which was used in the next reaction without further purification. Magnesium chips (320.8 mg,13.2 mmol) and magnetons were additionally added to a dried 100mL Schlenk flask while hot, the reactor was connected to a double tube, argon was purged 5 times, and the flask was cooled to room temperature. Then 10mL THF and 0.1mL DIBAL-H (dissolved in THF, 1M) were added to the Schlemk flask and stirred in a water bath at room temperature for 5 minutes, followed by 3, 5-bis (trimethylsilyl) 4-methoxybromobenzene (3.6454 g,11.0 mmol) and stirred in an ice bath at 0deg.C for 2 hours to give a freshly prepared Grignard reagent. 20mL of THF is added into a three-neck flask after the solvent is pumped down to dissolve the novel phosphonyl chloride intermediate, the mixture is placed in an ice bath at 0 ℃ and stirred for 5min, and simultaneously, the novel Grignard reagent is dripped into the flask and stirred for 30min. After half an hour the ice bath was removed and the reaction was resumed at room temperature for 12h. The reaction was quenched with HCl solution (2 m,20 ml), extracted 3 times with ethyl acetate, the organic phases were combined and washed 2 times with saturated NaHCO 3 and saturated NaCl each, dried over anhydrous Na 2SO4, and the solvent was rotary evaporated and purified by column chromatography on silica gel (petroleum ether: ethyl acetate=2:1) to give 254.6mg of white solid in yield 19％.1H NMR(400MHz,CDCl3)δ7.81(d,J＝11.2Hz,4H),7.65(d,J＝11.2Hz,4H),7.22(td,J＝8.0,3.2Hz,2H),6.84–6.71(m,4H),3.71(s,6H),3.70(s,6H),2.94(s,6H),0.24(s,36H),0.19(s,36H).13C NMR(101MHz,CDCl3)δ173.7(d,J＝3.0Hz),173.6(d,J＝3.0Hz),157.2(d,J＝14.1Hz),142.5(d,J＝11.1Hz),141.7(d,J＝10.1Hz),133.7,131.0(d,J＝9.1Hz),130.7(d,J＝9.1Hz),130.6,129.6,128.6,127.6,127.3(d,J＝15.2Hz),125.5(d,J＝13.1Hz),112.8(d,J＝1.0Hz),63.6,63.5,54.7,0.2.31P NMR(162MHz,CDCl3)δ28.1.HRMS(ESI)Calcd.for C66H105O8Si8P2[M+H]+:1311.5433;found:1311.5425.FTIR(cm-1):2951,1375,1247,1199,1103,833,746,688.
Step 2: 4-OMe-3,5-TMS Synthesis of MeO-BIPHEP (4 a): to a 10mL dry seal tube were added 6a (180.0 mg,0.14 mmol) and magneton, and the mixture was introduced into a double tube while hot, and after argon was purged 5 times, the mixture was cooled to room temperature, toluene (2 mL) was added for dissolution, and then Ti (OiPr) 4 (0.04 mL,0.14 mmol) and TMDS (0.25 mL,1.4 mmol) were added, and after sealing the seal tube, the mixture was stirred in an oil bath at 100℃for 10 hours to give a black solution. After the reaction was completed and the tube was cooled to room temperature, washed with 20mL of DCM and transferred to a 100mL round bottom flask, quenched with NaOH solution (1 m,10 mL), extracted 2 times with DCM, the organic phases were combined and washed 2 times each with saturated NH 4 Cl and saturated NaCl, dried over anhydrous Na 2SO4, and purified by column chromatography on silica gel (petroleum ether: ethyl acetate=40:1) after rotary evaporation of the solvent to give 162.3mg of white solid in yield 91％.1H NMR(400MHz,CDCl3)δ7.38–7.30(m,8H),7.23(d,J＝8.0Hz,2H),6.75(d,J＝7.2Hz,2H),6.63(d,J＝7.6Hz,2H),3.67(s,6H),3.66(s,6H),2.97(s,6H),0.21(s,36H),0.15(s,36H).13C NMR(101MHz,CDCl3)δ172.1,171.2,157.7(d,J＝6.1Hz),144.4(d,J＝11.1Hz),142.5(d,J＝11.1Hz),140.5–140.3(m),133.5–133.2(m),132.7(d,J＝20.2Hz),131.5–131.3(m),130.7(t,J＝2.0Hz),130.7(t,J＝3.0Hz),128.2,125.9,63.6,63.5,55.0,0.3,0.3.31P NMR(162MHz,CDCl3)δ-16.9.HRMS(ESI)Calcd.for C66H105O6Si8P2[M+H]+:1279.5535;found:1279.5529.FTIR(cm-1):2951,1375,1245,1100,1011,832,750,688.
Example 2: synthesis of 4c
Step 1: synthesis of Compound 7: 1, 3-dibromo-5- (trimethylsilyl) benzene (6.18 g,20.0 mmol), anhydrous tetrahydrofuran (60 mL) was added to a dry 100mL Schlenk flask under argon, stirred for five minutes, the flask was placed in a-78deg.C cold bath, n-butyllithium solution (2.5M, 8.3mL,20.8 mmol) was added dropwise, and the reaction was continued at this temperature for 2 hours, followed by triisopropylsilicon chloride (4.9 mL,22.8 mmol). The reaction flask was returned to room temperature and reacted for 12 hours, and then quenched with saturated aqueous ammonium chloride (20 mL), the organic phase was extracted with ethyl acetate after separation, and the organic phase was washed twice with saturated aqueous sodium chloride, dried over anhydrous sodium sulfate, and the solvent was drained and then used directly for the next reaction. Magnesium turnings (729.2 mg,30.0 mmol) were added to another 100mL dry three-necked flask under argon atmosphere, tetrahydrofuran (20 mL) was dried, and diisobutylaluminum hydride solution (1M, 0.1 mL) was stirred at room temperature for 5 minutes. The above product was put into a three-necked flask, and the flask was placed in a room temperature water area to react for 2 hours. The three-necked flask was then placed in an ice-water bath at 0℃and diethyl phosphite (1.1 mL,8.0 mmol) was added thereto, followed by stirring for 0.5 hours and then returning to room temperature for reaction for 12 hours. Quenching the reaction by adding hydrochloric acid (2M, 20 mL), separating the solution, extracting the aqueous phase with ethyl acetate twice, mixing the organic phases, washing twice with saturated sodium bicarbonate aqueous solution and saturated sodium chloride aqueous solution, drying the organic phase with anhydrous sodium sulfate, and separating the organic phase by silica gel column chromatography after spin-drying the solvent (ethyl acetate: petroleum ether=1:8) to obtain colorless oily substance (2.71g,51％).1H NMR(400MHz,CDCl3)δ8.10(d,J＝474.4Hz,1H),7.87(d,J＝13.2Hz,2H),7.82–7.79(m,3H),7.60(d,J＝14.0Hz,2H),1.34(hept,J＝7.6Hz,6H),1.00(d,J＝7.6Hz,18H),0.99(d,J＝7.6Hz,18H),0.25(s,18H).13C NMR(101MHz,CDCl3)δ144.3,140.0(d,J＝9.1Hz),137.5(d,J＝12.1Hz),135.5(d,J＝10.1Hz),134.7(d,J＝9.1Hz),130.0(d,J＝99.0Hz).31P NMR(162MHz,CDCl3)δ24.8.HRMS(ESI)Calcd.for C36H68OPSi4[M+H]+:659.4079;found:659.4081.FTIR(cm-1):2946,2864,1462,1250,1016,947,835,675.
Step 2: synthesis of Compound 8: to a 100mL three-necked flask was added compound 7 (2.64 g,1.34 mmol) and an aqueous sodium hydroxide solution (5M, 16 mL), and the three-necked flask was placed in an oil bath at 100℃and heated under reflux, and an aqueous hydrogen peroxide solution (30% w/w,10 mL) was added to react at 100℃for 3 hours. After the reaction system is cooled to room temperature, the reaction bottle is placed in an ice water bath at 0 ℃, concentrated hydrochloric acid is added until white solid is not regenerated in the system. The reaction solution was filtered, the white solid was dissolved with ethyl acetate, the reaction system was extracted with ethyl acetate for 2 times, the organic phases were combined, washed twice with a saturated aqueous sodium bicarbonate solution and a saturated aqueous sodium chloride solution, and the solvent was dried by spinning to obtain a white solid. The resulting white solid was added to a dry 100mL three-necked flask under argon atmosphere, and toluene (20 mL) was added to dissolve. Thionyl chloride (6 mL) was added with heating in an oil bath at 80deg.C and heated to reflux for 3 hours. After the completion of the reaction, the solvent was drained, tetrahydrofuran (10 mL) was added under argon atmosphere to dissolve, and a tetrahydrofuran solution (1 m,6.5 mL) of 3-methoxy-phenylmagnesium bromide was added under an ice bath at 0 ℃, followed by resumption of the reaction at room temperature for 12 hours. The three-necked flask was placed in an ice-water bath at 0℃and quenched by the addition of dilute hydrochloric acid (2M, 20 mL). After separation, the aqueous phase was extracted three times with ethyl acetate, the organic phases were combined, and the organic phases were washed twice with saturated aqueous sodium bicarbonate and saturated aqueous sodium chloride. The organic phase was dried over anhydrous sodium sulfate, and purified by silica gel column chromatography after spin-drying the solvent (ethyl acetate: petroleum ether=1:2) to give a colorless oil (1.03g,41％).1H NMR(400MHz,CDCl3)δ7.98(dd,J＝1.4Hz,1H),7.95(dd,J＝1.4Hz,1H),7.80–7.73(m,2H),7.36–7.27(m,4H),7.11–7.02(m,2H),3.76(s,3H),1.23(hept,J＝7.2Hz,6H),0.93(d,J＝7.2Hz,18H),0.93(d,J＝7.2Hz,18H),0.22(s,18H).13C NMR(101MHz,CDCl3)δ159.7(d,J＝15.2Hz),143.8(d,J＝3.0Hz),139.8(d,J＝9.1Hz),139.4(d,J＝12.1Hz),136.8(d,J＝9.1Hz),134.7,133.8(d,J＝9.1Hz),130.9(d,J＝101.0Hz),129.4(d,J＝14.1Hz),124.7(d,J＝10.1Hz),118.8(d,J＝3.0Hz),116.1(d,J＝11.1Hz),55.5,18.50,18.48,10.7,-1.1.31P NMR(162MHz,CDCl3)δ33.2.HRMS(ESI)Calcd.for C43H74O2Si4P[M+H]+:765.4498;found:765.4492.FTIR(cm-1):2924,2863,1462,1250,1132,838,755,679.
Step 3: synthesis of compound 6 b: compound 8 (1.03 g,1.3 mmol) was added to a dry 100mL Schlenk flask under argon atmosphere and tetrahydrofuran (20 mL) was dried. The reaction flask was placed in a-78deg.C cold bath, a solution of lithium diisopropylamide in tetrahydrofuran (1M, 1.8 mL) was added, and the reaction was allowed to proceed at that temperature for 2 hours. A tetrahydrofuran solution of ferric chloride (304.9 mg,1.9mmol in 10mL tetrahydrofuran) was added to the flask, and the flask was then returned to room temperature for reaction for 12 hours. After the completion of the reaction, the reaction mixture was diluted with 20mL of methylene chloride, and quenched by the addition of aqueous NaOH (2M, 30 mL). The precipitate was filtered, the aqueous phase was extracted 3 times with dichloromethane, the organic phases were combined and washed 2 times with saturated aqueous ammonium chloride and saturated aqueous sodium chloride, the organic phase was dried over anhydrous sodium sulfate, and the solvent was rotary evaporated and purified by column chromatography on silica gel (ethyl acetate: petroleum ether=1:8) to give 415.7mg of pale yellow solid in yield 40％.1H NMR(400MHz,CDCl3)δ8.23(d,J＝11.6Hz,2H),7.95(d,J＝10.8Hz,2H),7.76–7.68(m,4H),7.64–7.58(m,2H),7.26–7.15(m,4H),6.87–6.77(m,4H),2.87(s,6H),1.29(hept,J＝7.6Hz,6H),1.19(hept,J＝7.6Hz,4H),1.00(d,J＝7.6Hz,18H),0.98(d,J＝7.6Hz,18H),0.88(d,J＝7.6Hz,18H),0.87(d,J＝7.6Hz,18H),0.22(s,18H),0.06(s,18H).13C NMR(101MHz,CDCl3)δ157.3(d,J＝14.1Hz),142.7(d,J＝11.1Hz),139.3(d,J＝9.1Hz),139.1(d,J＝9.1Hz),138.9(d,J＝11.1Hz),138.3(d,J＝8.1Hz),138.2(d,J＝9.1Hz),137.0(d,J＝8.1Hz),135.1(d,J＝103.0Hz),132.9(d,J＝8.1Hz),132.6,131.9(d,J＝8.1Hz),131.8,131.6,130.8,126.7(d,J＝15.2Hz),125.8(d,J＝12.1Hz),112.6,54.5,18.6,18.53,18.47,18.46,10.7,10.6,-1.1,-1.2.31P NMR(162MHz,CDCl3)δ30.6.HRMS(ESI)Calcd.for C86H145O4Si8P2[M+H]+:1527.8767;found:1527.8776.FTIR(cm-1):2944,2864,1460,1250,857,835,752,674.
Step 4: synthesis of Compound 4 c: to a dried 10mL vial under argon was added compound 6b (152.9 mg,0.1 mmol), mesitylene (1 mL), triethylamine (0.2 mL). The tube was placed in an ice-water bath at 0℃and trichlorosilane (0.1 mL,1.0 mmol) was added dropwise thereto, and after the tube was sealed with a polytetrafluoroethylene plug after no more gas was produced in the tube, the tube was reacted in an oil bath at 120℃for 12 hours. After 12 hours, the tube was placed in an ice-water bath at 0℃and an aqueous sodium hydroxide solution (25%, 2 mL) was added under argon atmosphere, and the mixture was sealed with a polytetrafluoroethylene plug and reacted in an oil bath at 80℃for 1 hour. After the reaction solution was cooled to room temperature, the reaction solution was extracted 3 times with methylene chloride, and the organic phases were combined. The organic phase was washed twice with saturated ammonium chloride solution and saturated sodium chloride solution. The organic phase was dried over anhydrous sodium sulfate, and purified by silica gel column chromatography (ethyl acetate: petroleum ether=1:50) after the solvent was drained to give 140.7mg of a white solid in yield 94％.1H NMR(400MHz,CDCl3)δ7.56(s,2H),7.51(dd,J＝2.8Hz,2H),7.44(dd,J＝4.4Hz,2H),7.39(s,2H),7.35(s,2H),7.26–7.23(m,2H),7.18(dd,J＝8.0Hz,2H),6.84(d,J＝6.8Hz,2H),6.64(d,J＝8.4Hz,2H),2.83(s,6H),1.31(hept,J＝7.6Hz,6H),1.18(hept,J＝7.6Hz,6H),1.01(d,J＝7.6Hz,18H),0.99(d,J＝7.6Hz,18H),0.90(d,J＝7.6Hz,18H),0.87(d,J＝7.6Hz,18H),0.18(s,18H),0.03(s,18H).13C NMR(101MHz,CDCl3)δ157.8(t,J＝6.1Hz),142.9(t,J＝14.1Hz),140.7,140.4(t,J＝8.1Hz),140.1(t,J＝2.0Hz),139.5(t,J＝9.1Hz),138.9,138.6(dd,J＝9.1,7.1Hz),138.3(t,J＝2.0Hz),137.7(t,J＝2.1Hz),137.4(t,J＝11.1Hz),134.4(t,J＝8.1,6.1Hz),133.7(t,J＝20.2Hz),132.9(t,J＝4.0Hz),132.5,128.0,127.1,111.3,55.1,18.72,18.70,18.69,18.66,10.87,10.81,-1.0,-1.1.31P NMR(162MHz,CDCl3)δ-14.4.HRMS(ESI)Calcd.for C86H145Si8P2[M+H]+:1495.8868;found:14958883.FTIR(cm-1):2944,2864,1461,1250,1140,856,834,674.
Example 3: preparation of Complex A
In an argon glove box, [ Ir (COD) Cl ] 2 (67.2 mg,0.1 mmol), SEGPHOS (122.1 mg,0.2 mmol) and dry toluene (15 mL) were added to a 25mL dry seal, and the seal was closed and heated in an oil bath at 60℃for 4 hours. After the tube was sealed and cooled, the reaction solution was filtered in an argon glove box, and the solvent was drained to give 141.3mg of an orange-red solid in 84% yield. 31P NMR(162MHz,CDCl3) δ13.7.
Example 4: preparation of Complex B
In an argon glove box, [ Ir (COD) Cl ] 2 (3.4 mg, 5. Mu. Mol), DTMS-MeO-BIPHEP (11.0 mg,0.01 mmol) and dry toluene (1 mL) were added to a 10mL dry seal, and the seal was closed and heated in an oil bath at 40℃for 10 hours. And after the tube is sealed and cooled, the yellow solid of the solvent is pumped out, and the reaction nuclear magnetic yield is 95%. 31P NMR(162MHz,CDCl3)δ-3.47(d),-9.04(d),(2Jpp =37.3 Hz).
Example 5: cumene transfer dehydrogenation reaction
The reaction mixture was sampled and subjected to gas chromatography detection using commercially available t-butylethylene 1a as a hydrogen acceptor (10 mmol,1.0 equiv), cumene 2a (50 mmol,5.0 equiv) as a dehydrogenation starting material, DTMSM-MeO-BIPHEP 4a (0.005 mmol,0.05% equiv.) as a ligand, and [ Ir (cod) Cl ] 2 (0.0025 mmol,0.025% equiv.) as an iridium source, followed by iridium-catalyzed selective alkane transfer dehydrogenation reaction, cooling the reaction mixture to room temperature (25-30 ℃), and the yield of the corresponding α -methylstyrene compound 3a was 71%, catalytic conversion number 1420. Retention time: t R (t-butylethylene) =2.82 min, t R (t-butylethane) =2.86 min, t R (cumene) =5.41 min, t R (α -methylstyrene) )＝5.97min.(1H NMR(400MHz,CDCl3)δ7.46–7.43(m,2H),7.32–7.28(m,2H),7.25–7.22(m,1H),5.36(d,J＝0.8Hz,1H),5.09–5.05(m,1H),2.14(dd,J＝1.6,0.8Hz,3H).
Example 6: cumene transfer dehydrogenation reaction
The reaction mixture was sampled and subjected to gas chromatography using commercially available t-butylethylene 1a as a hydrogen acceptor (10 mmol,1.0 equiv), cumene 2a (50 mmol,5.0 equiv) as a dehydrogenation starting material, DTMS-SYNPHOS b (0.005 mmol,0.05% equiv.) as a ligand, and [ Ir (cod) Cl ] 2 (0.0025 mmol,0.025% equiv.) as an iridium source, and by iridium-catalyzed selective alkane transfer dehydrogenation, after cooling the reaction mixture to room temperature (25-30 ℃), the yield of the corresponding α -methylstyrene compound 3a was 55%, and the catalytic conversion number was 1093. Retention time: t R (t-butylethylene) =2.82 min, t R (t-butylethane) =2.86 min, t R (cumene) =5.41 min, t R (α -methylstyrene) )＝5.97min.1H NMR(400MHz,CDCl3)δ7.46–7.43(m,2H),7.32–7.28(m,2H),7.25–7.22(m,1H),5.36(d,J＝0.8Hz,1H),5.09–5.05(m,1H),2.14(dd,J＝1.6,0.8Hz,3H).
Example 7: cumene transfer dehydrogenation reaction
With commercially available tert-butylethylene 1a as hydrogen acceptor (10 mmol,1.0 equiv), cumene 2a (50 mmol,5.0 equiv) as dehydrogenation feed, 3-TIPS-5-TMS-MeO-BIPHEP 4c (0.005 mmol,0.05% equiv.) as ligand,
[ Ir (cod) Cl ] 2 (0.0025 mmol,0.025% equiv.) was used as iridium source, and the reaction solution was cooled to room temperature (25-30 ℃ C.) and sampled for gas chromatography detection, the yield of the corresponding alpha-methylstyrene compound 3a was 74%, the catalytic conversion number 1478, by iridium-catalyzed selective alkane transfer dehydrogenation. Retention time: t R (t-butylethylene) =2.82 min, t R (t-butylethane) =2.86 min, t R (cumene) =5.41 min, t R (α -methylstyrene) )＝5.97min.1H NMR(400MHz,CDCl3)δ7.46–7.43(m,2H),7.32–7.28(m,2H),7.25–7.22(m,1H),5.36(d,J＝0.8Hz,1H),5.09–5.05(m,1H),2.14(dd,J＝1.6,0.8Hz,3H).
Example 8: transfer dehydrogenation of 2, 2-dimethyl-3-phenylbutane
Using commercially available tert-butylethylene 1a as starting material hydrogen acceptor (0.4 mmol,1.0 equiv), 2-dimethyl-3-phenylbutane 2d (0.4 mmol,1.0 equiv) as dehydrogenation starting material, [ DTMSM-MeO-BIPHEP 4a (0.04 mmol,10% equiv) as ligand, [ Ir (cod) Cl ] 2 (0.02 mmol,5% equiv) as iridium source, toluene (1 mL) as solvent through iridium-catalyzed selective alkane transfer dehydrogenation reaction, cooling the reaction solution to room temperature, sampling and gas chromatography detection, yield of the corresponding 3, 3-dimethyl-2-phenyl-1-butene compound 3d was 42%. t R (tert-butylethylene) =3.24 min, t R (tert-butylethane) =3.33 min, t R (3, 3-dimethyl-2-phenyl-1-butene) =16.32 min, t R (2, 2-dimethyl-3-phenylbutane) )＝16.56min.1H NMR(400MHz,CDCl3)δ7.33-7.25(3H,m),7.15(2H,dd,J＝8.0,1.6Hz),5.18(1H,d,J＝1.6Hz),4.78(1H,d,J＝1.6Hz),1.06(9H,s).
Example 9:1, 1-diphenylethane transfer dehydrogenation
The commercial tert-butylethylene 1a was used as hydrogen acceptor (0.4 mmol,1.0 equiv), 1-diphenylethane 2e (0.4 mmol,1.0 equiv) was used as dehydrogenation starting material, DTMSM-MeO-BIPHEP 4a (0.008 mmol,2% equiv) was used as ligand, [ Ir (cod) Cl ] 2 (0.04 mmol,1% equiv) was used as iridium source, toluene (1 mL) was used as solvent for iridium-catalyzed selective alkane transfer dehydrogenation reaction, the reaction solution was cooled to room temperature, and samples were taken for gas chromatography detection, corresponding 1, 1-diphenylethylene compound 3d was 65%. t R (t-butylethylene) =3.72 min, t R (t-butylethane) =3.80 min, t R (1, 1-diphenylethane) =17.91 min, t R (1, 1-diphenylethylene) =17.98 min. 1H NMR(400MHz,CDCl3 ) Delta 7.29-7.21 (m, 10H), 5.38 (s, 2H).
Example 10: 1-isopropyl adamantane transfer dehydrogenation reaction
With commercially available tert-butylethylene 1a as hydrogen acceptor (1.5 mmol,1.0 equiv), 1-isopropyladamantane 2f (5 mmol,3.3 equiv) as dehydrogenation starting material, DTMSM-MeO-BIPHEP 4a (0.005 mmol,0.33% equiv.) as ligand, [ Ir (cod) Cl ] 2 (0.0025 mmol,0.17% equiv.) as iridium source, the reaction solution was cooled to room temperature, sampled and subjected to gas chromatography detection, the yield of the corresponding 2- (1-adamantyl) -propene compound 3f was 97%. t R (t-butylethylene) =3.72 min, t R (t-butylethane) =3.80 min, t R (1-isopropyladamantane) =17.41 min, t R (2- (1-adamantyl) -propylene )＝17.43min.1H NMR(400MHz,CDCl3)δ4.70–4.66(m,2H),2.00(s,3H),1.75–1.71(m,6H),1.68–1.64(m,9H).
Example 11: 1-isopropyl adamantane transfer dehydrogenation reaction
With commercially available tert-butylethylene 1a as hydrogen acceptor (1.5 mmol,1.0 equiv), 1-isopropyladamantane 2f (5 mmol,3.3 equiv) as dehydrogenation starting material, 3-TIPS-5-TMS-MeO-biphen ep 4c (0.005 mmol,0.33% equiv.) as ligand, [ Ir (cod) Cl ] 2 (0.0025 mmol,0.17% equiv.) as iridium source, the reaction was subjected to iridium-catalyzed selective alkane transfer dehydrogenation reaction, the reaction solution was cooled to room temperature, sampled and subjected to gas chromatography detection, the yield of the corresponding 2- (1-adamantyl) -propene compound 3f was 97%. t R (t-butylethylene) =3.29 min, t R (t-butylethane) =3.38 min, t R (1-isopropyladamantane) =17.41 min, t R (2- (1-adamantyl) -propylene )＝17.43min.1H NMR(400MHz,CDCl3)δ4.70–4.66(m,2H),2.00(s,3H),1.75–1.71(m,6H),1.68–1.64(m,9H).
Comparative example 1: cumene transfer dehydrogenation reaction
The catalyst was prepared from commercially available t-butylethylene 1a (10 mmol,1.0 equiv), cumene 2a (50 mmol,5.0 equiv), DTBM-SEGPHOS (0.005 mmol,0.05% equiv.) as ligand, and [ Ir (cod) Cl ] 2 (0.0025 mmol,0.025% equiv.) as iridium source by iridium-catalyzed selective alkane transfer dehydrogenation, cooling the reaction solution to room temperature, sampling and gas chromatography detection, the yield of the corresponding alpha-methylstyrene compound 3a was 50%, and the catalytic conversion number was 992. Retention time: t R (t-butylethylene) =2.82 min, t R (t-butylethane) =2.86 min, t R (cumene) =5.41 min, t R (α -methylstyrene) )＝5.97min.1H NMR(400MHz,CDCl3)δ7.46–7.43(m,2H),7.32–7.28(m,2H),7.25–7.22(m,1H),5.36(d,J＝0.8Hz,1H),5.09–5.05(m,1H),2.14(dd,J＝1.6,0.8Hz,3H).
Comparative example 2: transfer dehydrogenation of 2, 2-dimethyl-3-phenylbutane
The commercial tert-butylethene 1a was used as starting material hydrogen acceptor (0.4 mmol,1.0 equiv), 2-dimethyl-3-phenylbutane 2d (0.4 mmol,1.0 equiv) was used as dehydrogenation starting material, DTBM-SEGPHOS (0.04 mmol,10% equiv) was used as ligand, [ Ir (cod) Cl ] 2 (0.02 mmol,5% equiv) was used as iridium source, toluene (1 mL) was used as solvent for iridium-catalyzed selective alkane transfer dehydrogenation reaction, the reaction solution was cooled to room temperature, and samples were taken for gas chromatography detection, the yield of the corresponding 3, 3-dimethyl-2-phenyl-1-butene compound 3d was 32%. t R (tert-butylethylene) =3.24 min, t R (tert-butylethane) =3.33 min, t R (3, 3-dimethyl-2-phenyl-1-butene) =16.32 min, t R (2, 2-dimethyl-3-phenylbutane) )＝16.56min.1H NMR(400MHz,CDCl3)δ7.33-7.25(3H,m),7.15(2H,dd,J＝8.0,1.6Hz),5.18(1H,d,J＝1.6Hz),4.78(1H,d,J＝1.6Hz),1.06(9H,s).
Comparative example 3: 1-isopropyl adamantane transfer dehydrogenation reaction
The reaction mixture was cooled to room temperature by iridium-catalyzed selective alkane transfer dehydrogenation using commercially available t-butylethylene 1a as a starting material (1.5 mmol,1.0 equiv), 1-isopropyladamantane 2f (5 mmol,3.3 equiv), DTBM-seghos (0.005 mmol,0.33% equiv.) as a ligand, and [ Ir (cod) Cl ] 2 (0.0025 mmol,0.17% equiv.) as an iridium source, and sampled for gas chromatography detection, with a yield of the corresponding 2- (1-adamantyl) -propene compound 3f of 84%. t R (t-butylethylene) =3.72 min, t R (t-butylethane) =3.80 min, t R (1-isopropyladamantane) =17.41 min, t R (2- (1-adamantyl) -propylene )＝17.43min.1H NMR(400MHz,CDCl3)δ4.70–4.66(m,2H),2.00(s,3H),1.75–1.71(m,6H),1.68–1.64(m,9H).

Claims (10)

1. A process for the preparation of an olefin compound, characterized in that it comprises the steps of: carrying out dehydrogenation reaction on a compound containing a fragment shown in a formula II-1 in the presence of a catalyst and a compound shown in a formula I to obtain a compound containing a fragment shown in a formula III-1;
R 10 and R 11 are independently C 1-C10 alkyl optionally substituted with 1,2 or 3R 10-1, C 6-C20 aryl optionally substituted with 1,2 or 3R 10 -2, C 1-C10 alkoxy optionally substituted with 1,2 or 3R 10-3, 1,2 or 3 heteroatoms optionally substituted with 1,2 or 3R 10-4 are independently selected from N, O and S, 1,2 or 3 5-9 membered heteroaryl having 1,2 or 3 heteroatoms, cycloalkyl of C 6-C12 optionally substituted with 1,2 or 3R 10-5 or 3 heteroatoms optionally substituted with 1,2 or 3R 10-6 are independently selected from N, O and S, 1,2 or 3, 3-6 membered heterocycloalkyl having 1,2 or 3 heteroatoms;
R 10-1、R10-2、R10-3、R10-4、R10-5 or R 10-6 are independently C 1-C6 alkyl or C 1-C6 alkoxy;
Wherein,
The compound shown as the formula I has the following structure:
R 1 is H, C 1-C10 alkyl optionally substituted with 1, 2 or 3R 1-1;
r 1-1 is C 1-C6 alkyl;
The catalyst comprises a metal complex formed by a compound shown as a formula IV-1 or IV-2 and iridium, and/or a mixture of the compound shown as the formula IV-1 or IV-2 and iridium;
r 2、R3、R4、R5、R6、R7、R8 and R 9 are independently H, C 1-C6 alkyl, C 1-C6 alkoxy or halogen;
R 12、R13、R18 and R 19 are independently H, C 1-C6 alkyl, C 1-C6 alkoxy or halogen;
Or R 14、R15 taken together with the atoms to which they are attached form a C 6-C10 aryl group, a C 6-C10 aryl group substituted with 1,2 or 3R A-1, a "6-12 membered heterocycloalkyl group having 1,2 or 3 heteroatoms" selected from N, O and S, or a "6-12 membered heterocycloalkyl group having 1,2 or 3 heteroatoms" substituted with 1,2 or 3R A-2, a "heteroatom selected from 1,2 or 3 heteroatoms" selected from N, O and S, a 6-12 membered heterocycloalkyl group having 1,2 or 3 heteroatoms;
Or R 16、R17 taken together with the atoms to which they are attached form a C 6-C10 aryl group, a C 6-C10 aryl group substituted with 1,2 or 3R A-1, a "6-12 membered heterocycloalkyl group having 1,2 or 3 heteroatoms" selected from N, O and S, or a "6-12 membered heterocycloalkyl group having 1,2 or 3 heteroatoms" substituted with 1,2 or 3R A-2, a "heteroatom selected from 1,2 or 3 heteroatoms" selected from N, O and S, a 6-12 membered heterocycloalkyl group having 1,2 or 3 heteroatoms;
Or R 15、R16 taken together with the atoms to which they are attached form a "heteroatom is O, a 7-13 membered heterocyclic ring having 2 heteroatoms" or a "heteroatom substituted with 1 or 2R A-3 is O, a 7-13 membered heterocyclic ring having 2 heteroatoms";
r A-1、RA-2 and R A-3 are independently C 1-C6 alkyl or C 1-C6 alkoxy or halogen;
ar 1 and Ar 2 are independently C 6-C10 aryl or C 6-C10 aryl substituted with 1-5R B-1;
R B-1 is independently C 1-C6 alkyl, C 1-C6 alkoxy or
R B-1-1、RB-1-2 and R B-1-3 are independently C 1-C6 alkyl;
Ar 3 and Ar 4 are independently C 6-C10 aryl or C 6-C10 aryl substituted with 1-5R B-2;
R B-2 is independently C 1-C6 alkyl, C 1-C6 alkoxy or
R B-1-1、RB-1-2 and R B-1-3 are independently C 1-C6 alkyl.
2. The process for producing an olefin compound according to claim 1, wherein one or more of the following conditions are satisfied;
(1) In the R 1, the C 1-C10 alkyl is C 1-C6 alkyl, preferably ethyl;
(2) In the R 1-1, the C 1-C6 alkyl is C 1-C4 alkyl, preferably methyl;
(3) In R 5 and R 6, the C 1-C6 alkoxy group is methoxy;
(4) In Ar 1 and Ar 2, the C 6-C10 aryl is phenyl;
(5) In the R B-1, the C 1-C6 alkoxy is methoxy;
(6) In R B-1-1、RB-1-2 and R B-1-3, the C 1-C6 alkyl groups are independently methyl or isopropyl;
(7) In R 10 and R 11, the C 1-C10 alkyl groups are independently C 1-C6 alkyl groups, preferably independently methyl, ethyl or n-hexyl;
(8) In R 10 and R 11, the cycloalkyl groups of C 6-C12 are independently 1-4 ring cycloalkanes, preferably 4 rings, more preferably adamantane;
(9) In R 10 and R 11, the C 6-20 aryl groups are independently C 6-10 aryl groups, preferably phenyl groups;
(10) In the R 10-1, the C 1-C6 alkyl is methyl;
(11) The R 14、R15、R16 and R 17 are the same, the heteroatom is selected from 1,2 or 3 of N, O and S, and the heteroatom is 1,2 or 3-12 membered heterocycloalkyl medium heteroatom is selected from O;
(12) The "heteroatom is selected from 1,2 or 3 of N, O and S, and the heteroatom number is 2 in 3-12 membered heterocycloalkyl of 1,2 or 3 of R 14、R15、R16 and R 17;
(13) R 14、R15、R16 and R 17, wherein the heteroatom is 1, 2 or 3 of N, O and S, and the 6-12 membered heterocycloalkyl in the 6-12 membered heterocycloalkyl with 1, 2 or 3 heteroatoms is 6 membered heterocycloalkyl;
And (14) Ar 3 and Ar 4, wherein the C 6-C10 aryl group is phenyl.
3. The process for producing an olefin compound according to claim 1, wherein one or more of the following conditions are satisfied;
(1) The R 10 and R 11 are independently C 1-C10 alkyl optionally substituted with 1, 2 or 3R 10-1, unsubstituted C 6-C20 aryl or unsubstituted C 6-C12 cycloalkyl; preferably C 1-C10 alkyl optionally substituted with 1, 2 or 3R 10-1 or unsubstituted C 6-C12 cycloalkyl;
(2) The R 1 is C 1-C10 alkyl optionally substituted with 2R 1-1;
(3) The R 2、R3、R4、R7、R8、R9、R12、R13、R18 or R 19 is independently H;
(4) The R 5 and R 6 are independently C 1-C6 alkoxy;
(5) The Ar 1 and Ar 2 are independently C 6-C10 aryl substituted with 2 or 3R B-1;
(6) The R B-1 groups are independently C 1-C6 alkoxy or
(7) The R 14、R15 together with the atoms to which they are attached form a "6-12 membered heterocycloalkyl having 1, 2 or 3 heteroatoms selected from 1, 2 or 3 of N, O and S";
(8) The R 16、R17 together with the atoms to which they are attached form a "6-12 membered heterocycloalkyl having 1, 2 or 3 heteroatoms selected from 1, 2 or 3 of N, O and S";
(9) Ar 3 and Ar 4 are independently C 6-C10 aryl substituted with 2R B-2;
(10) The R B-2 groups are independently
And (11) the compound containing the fragment represented by II-1 is a compound represented by II-1.
4. The process for producing an olefin compound according to claim 1, wherein one or more of the following conditions are satisfied;
(1) The compound containing the fragment shown in the formula II-1 is any one of the following compounds: A
(2) The compound containing the fragment shown in the formula III-1 is any one of the following compounds: A
And (3) the compound shown as formula I is
5. The method for producing an olefin compound according to claim 1, wherein the metal complex is
Wherein ,R2、R3、R4、R5、R6、R7、R8、R9、R12、R13、R14、R15、R16、R17、R18、R19、Ar1、Ar2、Ar3 and Ar 4 are as defined in any one of claims 1 to 4;
Preferably wherein Ar 3 and Ar 4 in formula A-1 are/>
6. The process for producing an olefin compound according to claim 1, wherein one or more of the following conditions are satisfied;
(1) The compound shown in the formula IV-1 is
(2) The compound shown in the formula IV-2 is
And (3) Ir is Ir +, preferably [ Ir (cod) Cl ] 2,[Ir(coe)2Cl]2 or [ Ir (C 2H4)2Cl]2), such as [ Ir (cod) Cl ] 2.
7. The process for producing an olefin compound according to claim 1, wherein one or more of the following conditions are satisfied;
(1) The molar ratio of the compound shown in the formula IV-1 or IV-2 to the compound shown in the formula I is (0.0005-0.1): 1; preferably (0.0005-0.05): 1; also preferred is 0.0005: 1. 0.0033: 1. 0.1:1 or 0.02:1, more preferably 0.0005:1 or 0.0033:1, particularly preferably 0.0033:1, a step of;
(2) In one embodiment, the molar ratio of iridium to the compound shown in formula I is (0.00025-0.05): 1; preferably 0.00025:1, 0.05:1, 0.01:1 or 0.0017:1, still preferably 0.00025:1 or 0.0017:1, more preferably 0.0017:1;
(3) The molar ratio of the compound containing the fragment shown in the formula II-1 to the compound shown in the formula I is (1-10): 1, preferably 5:1, 3.3:1 or 1:1, further preferably 5:1 or 3.3:1, and more preferably 3.3:1;
(4) The alkane transfer dehydrogenation reaction may be carried out in the presence of a solvent or in the absence of a solvent, and when the solvent is a benzene-based solvent, for example, one or more selected from toluene, xylene and trimethylbenzene, for example, toluene;
(5) The temperature of the alkane transfer dehydrogenation reaction is from 100 ℃ to 200 ℃, preferably from 150 ℃ to 200 ℃, for example 150 ℃;
(6) The alkane transfer dehydrogenation reaction time is 1min-24h; preferably 4h to 18h, for example 4h or 18h;
And (7) the reaction mass of the alkane transfer dehydrogenation reaction consists of: the compound shown in the formula I, the compound shown in the formula II-1 and the catalyst.
8. A compound shown as a formula IV-1,
Wherein,
R 2、R3、R4、R5、R6、R7、R8、R9、Ar1 and Ar 2 are as defined in any one of claims 1 to 3 or 6;
And the formula IV-1 satisfies the following condition: when Ar 1 and Ar 2 are simultaneously substituted with two R B-1, the compound of formula IV-1 described as having R B-1 not simultaneously is preferably
9. A complex;
Wherein ,R2、R3、R4、R5、R6、R7、R8、R9、R12、R13、R14、R15、R16、R17、R18、R19、Ar1、Ar2、Ar3 and Ar 4 are as defined in any one of claims 1 to 4; preferably wherein Ar 3 and Ar 4 in formula A-1 are
10. Use of a complex according to claim 9 in a dehydrogenation reaction according to any one of claims 1 to 7.
CN202410043645.7A 2024-01-11 2024-01-11 Method for preparing olefin by iridium-catalyzed alkane transfer dehydrogenation, ligand and complex Pending CN117886659A (en)

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