ye zhu 09/02/10 burgess’s group meeting
DESCRIPTION
Chiral Ligands On A Spiro Scaffold for Transition-Metal-Catalyzed Asymmetric Reactions Work by Prof. Zhou Qi-Lin. Ye Zhu 09/02/10 Burgess’s Group Meeting. Ubiquitous Spirocyclic Framework. - PowerPoint PPT PresentationTRANSCRIPT
![Page 1: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/1.jpg)
Ye Zhu09/02/10
Burgess’s Group Meeting
Chiral Ligands On A Spiro Scaffold for Transition-
Metal-Catalyzed Asymmetric Reactions
Work by Prof. Zhou Qi-Lin
![Page 2: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/2.jpg)
Ubiquitous Spirocyclic Framework
in 1900, von Baeyer introduced the name “spirocyclane” for bicyclic hydrocarbons having two rings with a common carbon atom (spiro carbon)
the two rings of the spiro compounds lie in perpendicular planes, which not only gives rise to an axial chirality in spiro compounds having substituents on the rings but also
increases molecular rigidity
racemization of chiral spiro compounds virtually impossible
very few applications despite these excellent characteristics
the spirocyclic framework is considerably more rigid than that ofbiaryls, since conformational changes involve distortion of the entire molecule
2
![Page 3: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/3.jpg)
Spiro[4,4]nonane-1,6-diol As Chiral Auxiliaries in the Reduction of
Ketones
Kumar, A., et al, Chem. Commun. 1992, 493.
2 eq. (+) 1, 2 eq. LAH, -80 °C, 80%, 98% ee2 eq. (+) 1, 2 eq. LAH, -20 °C, 75%, 89% ee
3
![Page 4: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/4.jpg)
Spiro[4,4]nonane-1,6-diol As Chiral Auxiliaries in the Reduction of
Ketones
Kumar, A., et al, Chem. Commun. 1992, 493.
2 eq. (+) 1, 2 eq. LAH, -80 °C, 80%, 98% ee2 eq. (+) 1, 2 eq. LAH, -20 °C, 75%, 89% ee
4
![Page 5: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/5.jpg)
Monodentate SpiroPhosphoramidite
Ligand
Xumu, Zhang, et al, Org. Lett. 2004, 3565.
5
![Page 6: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/6.jpg)
Synthesis of Chiral Monodentate Spiro Ligand via
9,9’-Spirobixanthene-1,1’-Diol
Xumu, Zhang, et al, Org. Lett. 2004, 3565.
6
![Page 7: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/7.jpg)
Synthesis of 1,1’Spirobiindane-7,7’-diol
Birman, V.B., et al, Tetrahedron Asymmetry 1999, 125.
7
![Page 8: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/8.jpg)
Birman, V.B., et al, Tetrahedron Asymmetry 1999, 125.
Synthesis of 1,1’Spirobiindane-7,7’-diol
8
![Page 9: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/9.jpg)
Highly efficient and practical resolution of1,1-spirobiindane-7,7-diol by inclusion
crystallization withN-benzylcinchonidinium chloride
Zhou, Qi-Lin, et al, Tetrahedron Asymmetry 2002, 1363.
A highly efficient and practical resolution of racemic
1,1-spirobiindane-7,7-diol (±)-1 has been achieved,
with the (S)-(−)- and (R)-(+)-forms of 1 obtained with
>99% e.e. in 82% yield from the inclusion complex and
75% yield from the mother liquor, respectively
9
![Page 10: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/10.jpg)
Synthesis of 9,9’-Spirobifluorene-1,1’-diol
Zhou, Qi-lin, et al,
10
![Page 11: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/11.jpg)
Synthesis of 9,9’-Spirobifluorene-1,1’-diol
SBIFOL was conveniently synthesized from 1,2-dibromobenzene and 3-bromoanisole in high yield. Both
enantiomers of SBIFOL were obtained in 99% ee by inclusion resolution with 2,3-dimethoxy-N,N,N’,N’
tetracyclohexylsuccinamide 11
![Page 12: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/12.jpg)
Synthesis of SDP Ligands
Zhou, Qi-Lin, et al, J. Am.Chem.Soc., 2003, 4404.
12
![Page 13: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/13.jpg)
Zhou, Qi-Lin, et al, Angew. Chem. Int. Ed., 2005, 1118.
Zhou, Q.-L. et al, Angew. Chem., Int. Ed. 2002, 41, 2348. Zhou, Q.-L. et al, Org. Lett. 2006, 8, 1479.
Zhou, Q.-L. et al, J. Org. Chem. 2004, 69, 8157.Zhou, Q.-L. et al, J. Am.Chem. Soc. 2006, 128, 11774.
Zhou, Q.-L. et al, Org. Lett. 2005, 7, 2333.
13
![Page 14: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/14.jpg)
Crystal Structures of Pd-complexes
14
![Page 15: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/15.jpg)
Synthesis of Chiral Spiro Phosphine-Oxazoline Ligands
Zhou, Q.-L. et al, J. Am.Chem. Soc. 2006, 128, 12886. 15
![Page 16: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/16.jpg)
Applications: Asymmetric Hydrogenation
ketones
a new chiral scaffold and their application in the ruthenium-catalyzed asymmetric hydrogenation of simple ketones with
high activity (S/C up to 100 000) and excellent enantioselectivity(ee up to 99.5%)
Zhou, Q.-L. et al, J. Am. Chem. Soc. 2006, 128, 11774
16
![Page 17: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/17.jpg)
Highly Enantioselective and Diastereoselective Synthesis of
Chiral Amino Alcohols
Zhou, Qi-Lin, et al, J. Am. Chem. Soc., 2010, 4222.17
![Page 18: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/18.jpg)
Enantioselective Hydrogenation of α-Arylmethylene Cycloalkanones
Zhou, Qi-Lin, et al, J. Am. Chem. Soc., 2010, 4538.
the asymmetric hydrogenation of exocyclicα,β-unsaturated ketones is a challenge task
18
![Page 19: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/19.jpg)
Applications: Asymmetric Hydrogenation
Zhou, Q.-L. et al, J. Am. Chem. Soc. 2007, 129, 1868aldehydes
the first example of asymmetric hydrogenation of aldehyde via DKR
19
![Page 20: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/20.jpg)
Applications: Asymmetric Hydrogenation
Zhou, Q.-L. et al, Angew. Chem. Int.Ed. 2005, 1118α,β-unsaturated carboxylic acid
these results are comparable to, or better than,those obtained with [Ru(OAc)2(binap)] and other catalysts
20
![Page 21: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/21.jpg)
Applications: Asymmetric Hydrogenation
Zhou, Q.-L. et al, Angew. Chem. Int.Ed. 2005, 1118
α,β-unsaturated carboxylic acid
these results represents the highest level of enantiocontrol reported to date in the asymmetric hydrogenation of cinnamic acid derivatives 21
![Page 22: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/22.jpg)
Applications: Asymmetric Hydrogenation
Zhou, Q.-L. et al, Adv. Synth, Catal. 2006, 1271α,β-unsaturated carboxylic acid
22
![Page 23: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/23.jpg)
Hydrogenations with Chiral Spiro Phosphine-Oxazoline Ligands
Zhou, Q.-L. et al, J. Am. Chem. Soc. 2006, 128,
12886.
Zhou, Q.-L. et al, J. Am. Chem. Soc. 2008, 130,
8584.
Zhou, Q.-L. et al, J. Am.
Chem. Soc. 2010, 132, 1172.
23
![Page 24: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/24.jpg)
Applications: Asymmetric Hydrogenation
enamines
24
![Page 25: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/25.jpg)
Applications: Asymmetric Hydrogenation
Other ligands such as the diphosphine ligands BINAP, Josiphos, and SDP (6a) and the monodentate phosphorus ligands Mono- Phos, H-MOP, SIPHOS (9a), and ShiP
(10a) provided the hydrogenation product with very low enantioselectivities under the same reaction conditions
Zhou, Q.-L. et al, J. Am. Chem. Soc. 2006, 128, 11774
25
![Page 26: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/26.jpg)
Iridium-Catalyzed Asymmetric Hydrogenation
of Cyclic Enamines
Zhou, Qi-Lin, et al, J. Am. Chem. Soc., 2010, 1366.26
![Page 27: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/27.jpg)
Enantioselective Iron-catalysed O–H Bond Insertions
Zhou, Qi-Lin, et al, Natural Chemistry, 2010, 546.
27
![Page 28: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/28.jpg)
Other Developments
Zhou, Qi-Lin, et al, J. Am. Chem. Soc., 2007, 5834. Enantioselective Insertion of Carbenoids into N−H Bonds Catalyzed by Copper Complexes of Chiral Spiro Bisoxazolines
Zhou, Qi-Lin, et al, Angew. Chem. Int. Ed., 2008, 932. Enantioselective Synthesis of a-Hydroxyesters by a Copper–Carbenoid O-H Insertion Reaction
28
![Page 29: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/29.jpg)
Other Developments
Zhou, Qi-Lin, et al, Angew. Chem. Int. Ed., 2008, 4351. Enantioselective Rhodium-Catalyzed Addition of Arylboronic Acids to β-Ketoesters
29
Zhou, Qi-Lin, et al, Angew. Chem. Int. Ed., 2008, 8496. Copper-Catalyzed Highly Enantioselective Carbenoid Insertion into Si-H Bonds
![Page 30: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/30.jpg)
Addition of Arylboronic Acids to Aldehydes and N-Tosylarylimines
30
![Page 31: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/31.jpg)
Ni Catalyzed Reactions
Zhou, Qi-Lin, et al, J. Am. Chem. Soc., 2010, 10955.Enantioselective Nickel-Catalyzed Reductive Coupling of Alkynes and Imines
Zhou, Qi-Lin, et al, J. Am. Chem. Soc., 2008, 14052.Enantioselective Nickel-Catalyzed Alkylative Coupling of Alkynes and Aldehydes
31
![Page 32: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/32.jpg)
Asymmetric hydrovinylat-
ion of VinylarenesZhou, Q.-L. et al, J. Am. Chem. Soc. 2006, 128,
2780
32
![Page 33: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/33.jpg)
Pd Catalyzed Carboamination Reactions
John, Wolfe, et al, J. Am. Chem. Soc. 2010, 12157. 33
![Page 34: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/34.jpg)
Possible Works
34
![Page 35: Ye Zhu 09/02/10 Burgess’s Group Meeting](https://reader035.vdocument.in/reader035/viewer/2022062301/56815d29550346895dcb2194/html5/thumbnails/35.jpg)
Thanks
35