CN102786453A - Chiral sulfoxide alkene ligand, preparation method and application thereof - Google Patents

Chiral sulfoxide alkene ligand, preparation method and application thereof Download PDF

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CN102786453A
CN102786453A CN2011101267815A CN201110126781A CN102786453A CN 102786453 A CN102786453 A CN 102786453A CN 2011101267815 A CN2011101267815 A CN 2011101267815A CN 201110126781 A CN201110126781 A CN 201110126781A CN 102786453 A CN102786453 A CN 102786453A
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alkene
chiral
reaction
sulfoxide
chiral sulfoxide
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万伯顺
薛峰
吴凡
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention relates to a chiral sulfoxide alkene ligand, a preparation method and an application thereof. According to the present invention, cheap and available 2-bromobenzyl bromide is adopted as a start material to obtain 2-bromobenzyl diethyl phosphate; then a Horner-Emmons reaction is adopted to introduce an alkene group; and finally lithiation modification is performed on bromine, and a corresponding chiral sulfoxide group is introduced. With the present invention, the target product is conveniently and rapidly synthesized through three steps; coordinate of the novel chiral sulfoxide alkene ligand and rhodium can be well used for catalysis of conjugate addition reactions on cyclic ketene, nitroalkene, and cyano alkene by aryl boronic acid, especially for an addition reaction on cyclic ketene by aryl boronic acid, wherein a good catalysis effect of the addition reaction on the cyclic ketene by the aryl boronic acid is provided.

Description

A kind of chiral sulfoxide alkene part and preparation thereof and application
Technical field
The present invention relates to the design of novel chiral sulfoxide alkene part and the preparation method of part.Also relate to above-mentioned part at the catalysis aryl boric acid to the application in the conjugate addition reaction of ring-type ketenes, nitroolefin and cyanic acid alkene.
Background technology
In chiral metal catalysis, one of its key problem is the synthetic good chiral ligand of ingenious design.For many years, people have obtained very big success and have been widely used in the asymmetric catalysis on synthetic various chiral ligands.Just in asymmetric catalysis, occupy an important position [document 1. (a) Masdeu-Bult ü, A.M of everybody the sulphur part known for example; D é guez, M; Maryin, E.; G ü mez, M.Coord.Chem.Rev.2003,242,159. (b) Fern á ndez, I.Khiar, N.Chem.Rev.2003,103,3651. (c) Mellah, M.; Voituriez, A.; Schulz, E.Chem.Rev.2007,107,5133. document 2. (a) Wang, C.; Wu, X.; Zhou, L.; Sun, J.Chem.Eurr.J.2008,14,8789. (b) Pei, D.; Zhang, Y.; Wei, S.; Wang, M; Sun, J.Adv.Synth.Catal.2008,350,619.], but wherein chiral sulfoxide mainly is to be used for asymmetric catalysis [document 3. (a) Fernandez, I. as the chirality prothetic group for a long time; Khiar, N.Chem.Rev.2003,103,3651. (c) Lin, G.Q.; Xu, M.H.; Zhong, Y.W; Sun, X.W.Acc.Chem.Res.2008,41,831.].[document 4.James, B.R. since Canadian James research group is first with chiral sulfoxide and metal Ru and the reaction of Rh coordination catalysis hydrogenation of olefin; McMillan, R.S.; Reimer; K.J.J.Mol.Catal.1976; 1,439.], the research worker successively designs multiple chiral sulfoxide parts such as synthetic two sulfoxide, sulfoxide phosphine, Ya Feng oxazoline both at home and abroad; In metal Pd and replacement of Cu catalysis allyl group and Diels-A1der reaction, good result (following formula 3) [document 5. (a) Chen, J.M have been made; Li, D.; Ma, H.F.; Cun, L.F.; Zhu, J.; Deng, J.G; Liao, J.Tetrahedron Lett.2008,49,6921. (b) Chen, J.M.; Lang, F.; Li, D.; Cun, L.F.; Zhu, J.; Deng, J.G; Liao, J.Tetrahedron:Asymmetry 2009,20,1953. (c) Wang, P.; Chen, J.M.; Cun, L.F.; Deng, J.G.; Liao, J.Org.Biomol.Chem.2009,7,3741. (d) Liao, J.; Sun, X.X.; Cui, X.; Yu, K.K.; Zhu, J.; Deng, J.G.Chem.Eur.J.2003,9,2611. (e) Lang, F.; Li, D.; Chen, J.M.; Chen, J.; Li, L.C.; Cun, L.F.; Zhu, J.; Deng, J.G.; Liao, J.Adv.Synth.Catal.asap (adsc.200900792). document 6. (a) Schenkel, L.B.; Ellman, J.A.Org.Lett.2003,5,545. (b) Owens, T.D.; Hollander, F.J.; Oliver, A.G.; Ellman, J.A.J.Am.Chem.Soc.2001,123,1539. (c) Bolm, C.; Martin, M.; Simic, O.; Verrucci, M.Org.Lett.2003,5,427. (d) Bolm, C.; Simic, O.J.Am.Chem.Soc.2001,123,3830. document 7. (a) Mariz, R.; Luan, X.J.; Gatti, M.; Linden, A.; Dorta, R.J.Am.Chem.Soc.2008,130,2172. (b) B ü rgi, J.; Mariz, R.; Gatti, M.; Drinkel, E.; Luan, X.J.; Blumentritt, S.; Linden, A.; Dorta, R.Angew.Chem.Int.Ed.2009,48,2768.].In recent years, woods Guoqiang and Xu Minghua, physiognomy secondary such as Hayashi and Carreira have been opened up novel chiral diene ligand [document 8. (a) Wang, Z.Q. with good rigidity conformational structure; Feng, C.G.; Xu, M.H.; Lin, G.Q.J.Am.Chem.Soc.2007,129,5336. (b) Feng, C.G.; Wang, Z.Q.; Shao, C.; Xu, M.H.; Lin, G.Q.Org.Lett.2008,10,4101. (c) Hu, X.C.; Cao, Z.P.; Liu, Z.Q.; Wang, Y.Z.; Du, H.F.Adv.Synth.Catal.2010, asap (adsc.200900693) document 9. (a) Shintan, R.; Okamoto, K.; Otomaru, Y.; Hayashi, T.J.Am.Chem.Soc.2005,127,54. (b) Fessard, T.C.; Andrews, S.P.; Carreira, E.M.Angew.Chem.Int.Ed.2007,46,9331. (c) Paquin, J.F.; Defiber, C.; Carreira, E.M.J.Am.Chem.Soc.2005,127,10850.] (following formula 4), pushed the research of olefin ligands catalysis asymmetric reaction to new height.
Figure BDA0000061559340000021
Formula 3 representational chiralitys are come sulfone part formula 4 representational diene ligands
For further using and the development olefin ligands; Give full play to other heteroatomic advantages, people combine alkene and phosphine, nitrogen ligand again dexterously in the recent period, develop novel chirality phosphine alkene, nitrence part (following formula 5 and following formula 6); Be applied to Rh (I) catalytic 1; The research of 4-conjugate addition and Ir (I) catalytic hydrogenation has also obtained good result [document 10. (a) Duan, W.L.; Iwamura, H.; Shintani, R.; Hayashi, T.J.Am.Chem.Soc.2007,129,2130. (b) Piras, E.; F.; R ü egger, H.; Stein, D.;
Figure BDA0000061559340000023
M.; Gr ü tzmacher, H.Chem.Eur.J.2006,12,5849. document 11. (a) Maire, P.; Breher, H.;
Figure BDA0000061559340000024
H.; Gr ü tzmacher, H.Organometallics 2005,24,3207. (b) Hahn, B.T.; Tewes, F.;
Figure BDA0000061559340000025
R.; Glorius, F.Angew.Chem.Int.Ed.2010,49,1143. document 12. (a) Abel, E.W.; Dormer, J.C.; Ellis, D.; Orell, K.G.;
Figure BDA0000061559340000026
, V.; Hursthouse, M.B.; Mazid, M.A.J.Chem.Soc., Dalton Trans.1992,1073.], further abundant and developed the catalystsystem of olefine hybrid part.
Figure BDA0000061559340000027
Formula 5 representational chirality Phosphaalkene ligand formula 6 representational nitrence parts
At present; The application of chiral diene, phosphine alkene, nitrence part mainly concentrates on Rh (I) catalytic 1; On 4-conjugate addition and Ir (I) catalytic hydrogenation, the expansion of substrate and the extension of reaction type are needed further research (being limited to the conjugate addition [document 8-11] to ring-type ketenes and N-tosyl group aryl imine mostly like substrate); The catalyzed reaction type of sulfoxide part also mainly is confined to catalytic allyl group replacement of Pd and Cu and Diels-Alder reaction, and catalytic efficient also has much room for improvement.And the chiral sulfoxide alkene part that chiral olefin and sulfoxide part combine is not rightly also seen bibliographical information up to now.For giving full play to the strong chiral recognition ability of good steering capability of olefin ligands and sulfoxide part; This patent project is explored the applied research of the synthetic and asymmetric catalysis of the design of novel chiral sulfoxide alkene part; Further seek new efficient asymmetry catalysis system, disclose the characteristic that novel chiral sulfoxide alkene part carries out asymmetric catalysis.
Summary of the invention
The objective of the invention is to: design and synthesizing new chiral sulfoxide alkene part, replenish and the variety and uniqueness of development chiral ligand, it is catalytic 1 at Rh to set up chiral sulfoxide alkene part, the catalysis new system of 4-conjugation asymmetric reduction reaction,
1, the design that the present invention relates to novel chiral sulfoxide alkene part is synthesized, and is as shown in Figure 1.
2, the present invention relates to the chiral sulfoxide alkene part that synthesized; Its structure is suc as formula 1:
Figure BDA0000061559340000032
formula 1.
The preparation of said chiral sulfoxide alkene part: with adjacent bromobenzyl bromine is the beginning thing; Earlier with the triethyl-phosphite reaction; Obtain adjacent bromobenzyl diethyl phosphite, introduce olefin group through Horner-Emmons reaction subsequently, at last to the bromine lithiumation; Introduce corresponding chiral sulfoxide group with inferior semi-annular jade pendant acid esters of sulfo-and the reaction of inferior semi-annular jade pendant acid esters respectively, synthesize title product quickly and easily.
Described chiral sulfoxide alkene part at the catalysis aryl boric acid to the application in the conjugate addition reaction of ring-type ketenes, nitroolefin and cyanic acid alkene.
Said chiral sulfoxide alkene part, the chiral recognition ability that steering capability that olefin ligands is good and sulfoxide part are strong combines, and with metal-complexing the time, helps improving the antipodal faces recognition capability of reaction, produces good chiral environment; And through changing the substituting group of aromatic nucleus, can meticulous adjusting and the pi-conjugated state of p-that olefinic double bonds forms, improve the electron rich property of pair keys, strengthen the coordination ability (seeing shown in Figure 2) of itself and central metal.
This novel chiral sulfoxide alkene part and rhodium coordination can be used for the catalysis aryl boric acid preferably the conjugate addition reaction, particularly aryl boric acid of ring-type ketenes, nitroolefin and cyanic acid alkene have been obtained good catalytic effect to the addition of ring-type ketenes.
The present invention has following advantage:
1, the chiral sulfoxide alkene part that is designed is insensitive to water and air, and stable in properties is easy to preserve.
2, the part synthetic route is brief, and synthesis condition is gentle, can synthesize title product quickly and easily.
3, utilize the conjugate addition of this chiral sulfoxide alkene ligand catalysis aryl boric acid to nitroolefin and cyanic acid alkene, but the synthetic natural product of derivatize with physiologically active.
Description of drawings
The design of Fig. 1 novel chiral sulfoxide alkene part is synthetic;
Fig. 2 novel chiral sulfoxide alkene part and rhodium coordination.
Embodiment
With ligand 1 c in the formula 1 is example, and synthetic route is suc as formula 7:
Figure BDA0000061559340000042
The synthetic route of formula 7 chiral sulfoxide alkene ligand 1 c
Scheme?1.Synthesis?of?olefin-sulfoxide?ligand?1c.Reagents?and?conditions：a)P(OEt)3，160℃，5h；b)NaH，THF，0℃to?room?temperature，1h；then4-fluorobenzaldehyde，THF，0℃to?room?temperature，overnigh，89％；c)n-BuLi，THF，-78℃；then(R)-thiosulfinate，THF，-78℃to?room?temperature，overnight，52.3％.
The concrete operations step is following:
A): reference literature [Blake, Alexander J.; Harding, Mervyn; Sharp, John T.; .J.Chem.Soc., Perkin Transl.1994,3149-3162.]; The adjacent bromobenzyl bromine of 0.11mol (A) is dropped in the triethyl-phosphite of 0.14mol, slowly be warming up to 160 ℃, heat after 5 hours; Be cooled to room temperature; Slowly underpressure distillation, colourless oil liquid 33.6g (130-132 ℃, 1mmHg).Yield 92%.
B): under the ar gas environment, the adjacent bromobenzyl diethyl phosphite of 1mmol (B) is dropped among the THF of 2ml,, drip and finish at 0 ℃ of 60%NaH that slowly adds 1.2mmol down; Stirring at room 1 hour at 0 ℃ of 2mlTHF solution that slowly adds the p-Fluorobenzenecarboxaldehyde that contains 1.2mmol down, finishes stirred overnight at room temperature equally; Add the frozen water cancellation, with 3 * 3ml dichloromethane extraction 3 times, the merging organic phase; Use the saturated common salt water washing, anhydrous sodium sulfate drying is except that after desolvating; Make developping agent with sherwood oil and ETHYLE ACETATE, on silicagel column, carry out column chromatography, get target compound (C).Yield 89.5%.
C): under the ar gas environment, 1mmol (E)-1-is dropped into fluorobenzene ethene bromobenzene (C) among the THF of 2ml, the hexane solution of the n-Butyl Lithium of the 2.5M of slow dropping 0.4ml under-78 ℃ drips and finishes; Keep-78 ℃ and stirred 1 hour, at-78 ℃ of 2mlTHF solution that slowly add (the R)-thiosulfinate that contains 1mmol down, finish equally, heat up naturally; Stirred overnight adds the frozen water cancellation, with 3 * 3ml dichloromethane extraction 3 times, and the merging organic phase; Use the saturated common salt water washing, anhydrous sodium sulfate drying is except that after desolvating; Make developping agent with sherwood oil and ETHYLE ACETATE, on silicagel column, carry out column chromatography, get target compound.Yield 52.3%.
Aforementioned operation is the universal method of preparation part.
The employing p-Fluorobenzenecarboxaldehyde that provides except that above-mentioned synthetic enforcement formula 7 with (R)-the inferior semi-annular jade pendant acid esters of the tertiary butyl prepares the ligand 1 c; The preparation of other parts of the present invention; Can adopt the inferior semi-annular jade pendant acid esters of different substituting group phenyl aldehyde R and chirality, and synthesize by similar approach three steps that enforcement formula 7 is described.The first step (a) reaction all is to serve as the beginning thing with adjacent bromobenzyl bromine, with the triethyl-phosphite reaction, obtains adjacent bromobenzyl diethyl phosphite (seeing the first step (a) in the enforcement formula 8) earlier; Second step (b) was just passed through the olefin group that Horner-Emmons reaction introduces different substituents with different substituents phenyl aldehyde R under the NaH effect, obtain compound (C) (seeing the step of second in the enforcement formula 8 (b)); Final step (c) is carried out lithiumation with n-Butyl Lithium low temperature to bromine; Introduce corresponding chiral sulfoxide group (seeing the step of the 3rd in the enforcement formula 8 (c)) with the inferior semi-annular jade pendant acid esters reaction of different chiralitys respectively; Other condition is with above-mentioned enforcement; Thereby prepare other parts of the present invention, this is readily appreciated that for a person skilled in the art, therefore no longer enumerates the preparation instance of other chiral sulfoxide alkene parts.
Figure BDA0000061559340000061
Implement examination 8
The affirmation data of target compound:
Figure BDA0000061559340000062
1a：67.8％yield.white?solid.[α] D 20＝209.4(c＝1.1，CHCl 3). 1H?NMR(500MHz，CDCl 3)δ7.92(d，J＝7.1Hz，1H)，7.71(dd，J＝7.5，1.0Hz，1H)，7.54-7.45(m，5H)，7.39(t，J＝7.6Hz，2H)，7.31(t，J＝7.3Hz，1H)，7.06(d，J＝16.1Hz，1H)，1.18(s，9H).
13C?NMR(126MHz，CDCl 3)δ137.99(s)，136.91(s)，131.50(s)，131.26(s)，129.02(s)，128.46(s)，127.77(s)，126.89(s)，126.72(s)，125.58(s)，124.43(s)，64.72(s)，23.50(s).
Figure BDA0000061559340000063
1b：65.3％yield?colour-less?oil.[α] D 20＝186.5(c＝2.1，CHCl 3). 1H?NMR(400MHz，CDCl 3)δ7.90(d，J＝7.6Hz，1H)，7.68(d，J＝7.6Hz，1H)，7.52-7.39(m，4H)，7.36(d，J＝16.1Hz，1H)，7.01(d，J＝16.1Hz，1H)，6.92(d，J＝8.5Hz，2H)，3.83(s，3H)，1.18(s，9H).
13C?NMR(100MHz，CDCl 3)δ159.88(s)，138.14(d，J＝7.1Hz)，131.28(d，J＝15.3Hz)，131.01(d，J＝25.4Hz)，130.13(s)，129.59(s)，128.08(s)，127.27(s)，126.53(s)，125.20(s)，122.14(s)，114.37(s)，58.27(s)，55.41(s)，23.39(s).
1c：52.3％yield.white?solid.[α] D 20＝237.4(c＝1.0，CHCl 3). 1H?NMR(500MHz，CDCl 3)δ7.91(dd，J＝7.6，1.5Hz，1H)，7.71-7.66(m，1H)，7.52-7.45(m，4H)，7.42(d，J＝16.1Hz，1H)，7.08(t，J＝8.6Hz，2H)，7.02(d，J＝16.1Hz，1H)，1.18(s，9H).
13C?NMR(126MHz，CDCl 3)δ163.83(s)，161.86(s)，138.51(s)，137.80(s)，133.07(s)，131.28(s)，130.26(s)，128.41(d，J＝8.0Hz)，127.79(s)，126.74(s)，125.49(s)，124.19(s)，116.08(s)，115.90(s)，58.42(s)，23.44(s).
Figure BDA0000061559340000065
1d：66.6％yield?white?solid.[α] D 20＝220.5(c＝1.0，CHCl 3). 1H?NMR(400MHz，d6-Acetone)δ7.88(dd，J＝10.2，8.0Hz，2H)，7.65(dd，J＝12.2，9.5Hz，3H)，7.61-7.52(m，2H)，7.44(d，J＝8.5Hz，2H)，7.30(d，J＝16.2Hz，1H)，1.14(s，9H).
13C?NMR(100MHz，d6-Acetone)δ140.51(s)，132.13(s)，130.88(s)，129.92(s)，129.36(s)，128.68(s)，127.50(s)，126.44(s)，125.84(s)，58.58(s)，23.51(s).
Figure BDA0000061559340000071
1e：62.8％yield?white?solid.[α] D 20＝183.9(c＝1.0，CHCl 3). 1H?NMR(500MHz，CDCl 3)δ7.97-7.91(m，1H)，7.75-7.70(m，1H)，7.68-7.57(m，5H)，7.51(p，J＝7.3Hz，2H)，7.08(d，J＝16.1Hz，1H)，1.18(s，9H).
13C?NMR(126MHz，CDCl 3)δ140.27(s)，138.87(s)，137.27(s)，131.37(s)，130.20(s)，129.93(q，J C，F＝32.6Hz)129.88(s)，128.35(s)，126.95(s)，125.93(q，J C，F＝3.5Hz)，125.74(s)，124.21(d，J C，F＝272.4Hz)，58.48(s)，23.41(s).
Figure BDA0000061559340000072
1f：72.3％yield?white?solid.[α] D 20＝138.1(c＝1.1，CHCl 3). 1H?NMR(400MHz，d6-Acetone)δ7.81(d，J＝9.1Hz，1H)，7.65(d，J＝7.4Hz，1H)，7.53-7.43(m，2H)，6.77(d，J＝16.0Hz，1H)，6.36(d，J＝16.0Hz，1H)，1.14(s，9H)，1.13(s，9H).
13C?NMR(100MHz，d6-Acetone)δ206.26(s)，145.26(s)，139.28(s)，131.95(s)，127.83(s)，127.17(s)，126.45(s)，122.17(s)，58.73(s)，34.52(s)，23.65(s).
Figure BDA0000061559340000073
2a：59.1％yield.light-yellow?oil.[α] D 20＝124.2(c＝2.0，CHCl 3). 1H?NMR(400MHz，d 6-Acetone)δ7.85(d，J＝7.8Hz，2H)，7.58-7.49(m，2H)，7.46(d，J＝16.0Hz，1H)，7.22(dd，J＝9.0，7.0Hz，2H)，7.17(dd，J＝8.3，1.8Hz，1H)，6.98(d，J＝8.3Hz，1H)，3.88(s，3H)，3.84(s，3H)，1.14(s，9H).
13C?NMR(100MHz，d 6-Acetone)δ151.06(s)，150.74(s)，139.95(s)，139.05(s)，132.25(s)，132.02(s)，131.04(s)，127.99(s)，127.35(s)，126.05(s)，122.89(s)，121.06(s)，112.97(s)，111.06(s)，56.26(s)，30.58(s)，23.56(s).
2b：43.2％yield?white?solid.[α] D 20＝224.7(c＝1.1，CHCl 3). 1H?NMR(400MHz，CDCl 3)δ7.93(d，J＝16.4Hz，1H)，7.87(d，J＝7.8Hz，1H)，7.75(d，J＝7.8Hz，1H)，7.45(t，J＝7.5Hz，1H)，7.40(d，J＝9.7Hz，1H)，7.36(d，J＝8.1Hz，1H)，6.16(s，2H)，3.89(s，6H)，3.83(s，3H)，1.20(s，9H).
13C?NMR(100MHz，CDCl 3)δ161.26(s)，158.55(s)，139.68(s)，138.04(s)，130.98(s)，129.78(s)，127.50(s)，126.92(s)，126.59(s)，126.03(t，J＝18.7Hz)，125.33(s)，124.67(s)，123.15(s)，122.10(s)，107.36(s)，90.86(s)，90.58(s)，58.26(s)，55.90(s)，55.42(s)，55.26(s)，23.52(s).
Figure BDA0000061559340000075
3a：62.1％yield.white?solid.[α] D 20＝-199.7(c＝0.8，CHCl 3) 1H?NMR(500MHz，CDCl 3)δ7.92(dd，J＝7.3，1.9Hz，1H)，7.68(dd，J＝7.5，1.5Hz，1H)，7.48(tt，J＝11.1，3.7Hz，4H)，7.43(d，J＝16.1Hz，1H)，7.13-7.06(m，2H)，7.02(d，J＝16.1Hz，1H)，1.18(s，9H).
13C?NMR(126MHz，CDCl 3)δ163.86(s)，161.89(s)，138.63(s)，137.82(s)，133.13(s)，131.28(s)，130.26(s)，128.43(d，J＝8.1Hz)，127.81(s)，126.78(s)，125.50(s)，124.26(s)，116.10(s)，115.93(s)，58.41(s)，23.48(s).
Figure BDA0000061559340000076
3b：67.1％yield.white?solid.[α] D 20＝-115.9(c＝1.0，CHCl 3). 1H?NMR(500MHz，CDCl 3)δ8.01-7.96(m，1H)，7.61(dd，J＝5.9，3.1Hz，1H)，7.51(d，J＝8.2Hz，1H)，7.47-7.43(m，7H)，7.24(d，J＝8.1Hz，1H)，7.18(d，J＝8.1Hz，2H)，7.07(t，J＝8.6Hz，2H)，6.94(d，J＝16.1Hz，1H)，2.31(s，3H).
13C?NMR(126MHz，CDCl 3)δ163.88(s)，161.90(s)，143.05(s)，142.16(s)，141.54(s)，136.01(s)，132.97(s)，131.30(d，J＝13.1Hz)，130.07(s)，128.73(s)，128.50(d，J＝?8.1Hz)，126.13(s)，125.37(s)，124.96(d，J＝9.6Hz)，123.01(s)，115.97(d，J＝21.8Hz)，21.45(s).
Figure BDA0000061559340000081
3c：57.6％yield.[α] D 20＝-162.2(c＝0.6，CHCl 3). 1H?NMR(500MHz，CDCl 3)δ8.81(dd，J＝8.7，0.7Hz，1H)，8.36(dd，J＝8.0，1.2Hz，1H)，7.86(d，J＝9.0Hz，1H)，7.74(dd，J＝8.2，0.5Hz，1H)，7.57-7.50(m，2H)，7.47(d，J＝7.2Hz，1H)，7.42-7.36(m，2H)，7.07(d，J＝9.1Hz，1H)，6.96-6.83(m，5H)，6.63(d，J＝15.9Hz，1H)，3.71(s，3H)；
13C?NMR(126MHz，CDCl 3)δ163.40(s)，161.43(s)，157.55(s)，141.66(s)，135.06(s)，134.55(s)，132.82(s)，132.39(s)，130.09(s)，129.85(s)，129.20(s)，128.88(s)，128.49(s)，128.23(d，J＝8.0Hz)，127.30(s)，126.64(s)，125.62(s)，124.40(s)，123.74(s)，123.03(s)，122.61(s)，115.43(s)，115.26(s)，113.44(s)，56.54(s).
Figure BDA0000061559340000082
3d：65.7％yield.[α] D 20＝-291.1(c＝0.7，CHCl 3). 1H?NMR(500MHz，CDCl 3)δ8.06-8.01(m，1H)，7.59(dt，J＝9.0，4.5Hz，1H)，7.51-7.40(m，6H)，7.37(d，J＝16.0Hz，1H)，7.10-7.04(m，2H)，6.91(d，J＝16.0Hz，1H)，6.89-6.85(m，2H)，3.76(s，3H).
13C?NMR(126MHz，CDCl 3)δ163.77(s)，161.83(s)，142.90(s)，136.33(s)，135.71(s)，132.85(s)，131.20(s)，131.03(s)，128.56(s)，128.36(d，J＝8.1Hz)，127.48(s)，126.06(s)，124.54(s)，122.87(s)，115.94(s)，115.77(s)，114.76(s)，55.45(s).
In the target compounds of formula 1 part at the catalysis aryl boric acid to the application in the conjugate addition reaction of ring-type ketenes, nitroolefin and cyanic acid alkene.
(1): exemplary application is at the conjugate addition of catalysis aryl boric acid to the ring-type ketenes:
The concrete operations condition:
Under the ar gas environment, with 0.003mmol [RhCl (C 2H 4) 2] 2With the ligand 1 c of 0.0066mmol, join in the toluene of 1ml, room temperature reaction is after 1 hour.Add the ring-type ketenes (10) of 0.3mmol and the aryl boric acid of 0.45mmol again, add the toluene of 1ml, stir the KOH solution that adds the 0.75M of 0.2ml down again, finish, 40 ℃ were reacted 3 hours.Reaction is finished, be cooled to room temperature after, add 2mL methylene dichloride and 10mL water; Fully tell organic phase after the concussion, water is with 3 * 2mL dichloromethane extraction 3 times, merging organic phase; With the water washing of 10mL saturated common salt, anhydrous sodium sulfate drying is except that after desolvating; Make developping agent with sherwood oil and ETHYLE ACETATE, on silicagel column, carry out column chromatography, get target compound.
The affirmation data of representative target compound:
Figure BDA0000061559340000091
3-Phcnylcyclohexanone(12ae)：Colorless?oil.95％yield，92％ee，[α] D 20＝-12.6(c＝1.0，CHCl 3).R f＝0.45(petroleum?ether/EtOAc＝10/1).HPLC：Chiracel?AD-H?Column(250mm)，detected?at?210nm，20℃，n-hexane/i-propanol＝97/3，flow＝0.8mL/min(32bar)，retention?time?9.9min(major)and?11.8min(minor). 1H?NMR(500MHz，CDCl 3)δ7.39-7.28(m，2H)，7.26-7.19(m，3H)，3.01(tt，J＝11.8，3.9Hz，1H)，2.59(ddt，J＝14.0，4.2，1.9Hz，1H)，2.56-2.49(m，1H)，2.48-2.42(m，1H)，2.41-2.33(m，1H)，2.18-2.11(m，1H)，2.11-2.05(m，1H)，1.90-1.72(m，2H). 13C?NMR(126MHz，CDCl 3)δ211.05(s)，144.47(s)，128.79(s)，126.68(s)，49.04(s)，44.85(s)，41.29(s)，32.89(s)，25.64(s).
(2): exemplary application is at the conjugate addition of catalysis aryl boric acid to nitroolefin:
Figure BDA0000061559340000092
Under the ar gas environment, with 0.009mmol [RhCl (C 2H 4) 2] 2With 0.0099mmol part 3c, join in the methylene dichloride of 1ml, room temperature reaction is after 1 hour.Add the nitroolefin of 0.3mmol and the aryl boric acid of 0.45mmol again, add the methylene dichloride of 1ml, stir the pure water that adds 0.2ml down again, finish, 40 ℃ were reacted 12 hours.Reaction is finished, be cooled to room temperature after, add 2mL methylene dichloride and 10mL water; Fully tell organic phase after the concussion, water is with 3 * 2mL dichloromethane extraction 3 times, merging organic phase; With the water washing of 10mL saturated common salt, anhydrous sodium sulfate drying is except that after desolvating; Make developping agent with sherwood oil and ETHYLE ACETATE, on silicagel column, carry out column chromatography, get target compound.The affirmation data of representative target compound:
Figure BDA0000061559340000093
1-Methoxy-4-(2-nitro-1-phenylethyl)benzene.49％yield，colorless oil，[α] D20＝+12(C＝0.15，CHCl 3)for?69％ee.HPLC：Daicel?Chiralcel，AD-H，n-hexane/ethanol＝70/30，1.0mL/min，254nm，retention?time：8.5min(minor)，9.1min(major)1H?NMR(400MHz，CDCl 3)：7.41-7.31(m，6H)，7.26-7.21(m，1H)，6.89(d，2H，J＝8.6Hz)，5.22(d，2H，J＝7.9Hz)，4.88(t，1H，J＝8.2Hz)，3.76(s，3H).13C?NMR(100MHz，CDCl 3)：159.82，141.44，132.91，129.69，129.60，128.53，127.97，114.98，79.72，55.49，49.19.
(3): exemplary application is at the conjugate addition of catalysis aryl boric acid to cyanic acid alkene:
Figure BDA0000061559340000094
Under the ar gas environment, with 0.009mmol [RhCl (C 2H 4) 2] 2With the part 3b of 0.0099mmol, join in the toluene of 1ml, room temperature reaction is after 1 hour.Add the cyanic acid alkene of 0.3mmol and the aryl boric acid of 0.45mmol again, add the toluene of 1ml, stir the KHF that adds the 1.8M of 0.5ml down again 2Solution finishes, and 100 ℃ were reacted 12 hours.Reaction is finished, be cooled to room temperature after, add 2mL methylene dichloride and 10mL water; Fully tell organic phase after the concussion, water is with 3 * 2mL dichloromethane extraction 3 times, merging organic phase; With the water washing of 10mL saturated common salt, anhydrous sodium sulfate drying is except that after desolvating; Make developping agent with sherwood oil and ETHYLE ACETATE, on silicagel column, carry out column chromatography, get target compound.
The affirmation data of representative target compound:
Figure BDA0000061559340000101
1-Methoxy-4-(2-cynao-1-phenylethyl)benzene.24％yield，colorless?oil，[α] D20＝+20(C＝0.18，CHCl 3)for?60％ee.HPLC：Daicel?Chiralcel，OD-H，n-hexane/ethanol＝70/30，1.0mL/min，254nm，retention?time：16.5min(major)，18.2min(minor).1H?NMR(400MHz，CDCl 3)：7.35-7.31(m，2H)，7.26-7.21(m，3H)，7.15(d，2H，J＝8.5Hz)，6.86(d，2H，J＝8.5Hz)，4.33(t，1H，J＝7.7Hz)，3.76(s，3H)，2.99(d，2H，J＝7.7Hz). 13C?NMR(100MHz，CDCl 3)：158.86，136.44，132.91，129.69，129.60，128.53，127.97，117.77，114.98，55.8，38.2，27.6

Claims (4)

1. chiral sulfoxide alkene part, its structure as shown in the formula one of:
Figure FDA0000061559330000011
formula 1.
2. the preparation method of the said chiral sulfoxide alkene of claim 1 part; It is characterized in that: with adjacent bromobenzyl bromine is the beginning thing; With the triethyl-phosphite reaction, obtain adjacent bromobenzyl diethyl phosphite earlier, introduce olefin group through Horner-Emmons reaction subsequently; To the bromine lithiumation, introduce corresponding chiral sulfoxide group with inferior semi-annular jade pendant acid esters of sulfo-and the reaction of inferior semi-annular jade pendant acid esters respectively at last.
The described chiral sulfoxide alkene of claim 1 part at the catalysis aryl boric acid to the application in the conjugate addition reaction of ring-type ketenes, nitroolefin and cyanic acid alkene.
4. according to the described application of claim 3, it is characterized in that:
The said chiral sulfoxide alkene of claim 1 part, the chiral recognition ability that steering capability that olefin ligands is good and sulfoxide part are strong combines, and with metal-complexing the time, helps improving the antipodal faces recognition capability of reaction, produces good chiral environment; And through changing the substituting group of aromatic nucleus, can meticulous adjusting and the pi-conjugated state of p-that olefinic double bonds forms, improve the electron rich property of pair keys, strengthen the coordination ability of itself and central metal.
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CN103665036A (en) * 2013-11-22 2014-03-26 华中师范大学 Chiral sulfoxide-phosphine compound, preparation and appliance thereof
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