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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.

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Ye zhu 09 02 10 burgess s group meeting

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
Ubiquitous Spirocyclic Framework Transition-Metal-Catalyzed Asymmetric Reactions

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

the spirocyclic framework is considerably more rigid than that of

biaryls, since conformational changes involve distortion of the entire molecule

racemization of chiral spiro compounds virtually impossible

very few applications despite these excellent characteristics


Spiro 4 4 nonane 1 6 diol as chiral auxiliaries in the reduction of ketones
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% ee

2 eq. (+) 1, 2 eq. LAH, -20 °C, 75%, 89% ee


Spiro 4 4 nonane 1 6 diol as chiral auxiliaries in the reduction of ketones1
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% ee

2 eq. (+) 1, 2 eq. LAH, -20 °C, 75%, 89% ee


Monodentate spiro phosphoramidite ligand
Monodentate Spiro Reduction of KetonesPhosphoramidite Ligand

Xumu, Zhang, et al, Org. Lett. 2004, 3565.


Synthesis of chiral monodentate spiro ligand via 9 9 spirobixanthene 1 1 diol
Synthesis of Chiral Monodentate Spiro Ligand via Reduction of Ketones9,9’-Spirobixanthene-1,1’-Diol

Xumu, Zhang, et al, Org. Lett. 2004, 3565.


Synthesis of 1 1 spirobiindane 7 7 diol
Synthesis of 1,1’Spirobiindane-7,7’-diol Reduction of Ketones

Birman, V.B., et al, Tetrahedron Asymmetry1999, 125.


Synthesis of 1,1’Spirobiindane-7,7’-diol Reduction of Ketones

Birman, V.B., et al, Tetrahedron Asymmetry1999, 125.


Highly efficient and practical resolution of Reduction of Ketones1,1-spirobiindane-7,7-diol by inclusion crystallization withN-benzylcinchonidinium chloride

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

Zhou, Qi-Lin, et al, Tetrahedron Asymmetry2002, 1363.


Synthesis of 9 9 spirobifluorene 1 1 diol
Synthesis of 9,9’-Spirobifluorene-1,1’-diol Reduction of Ketones

Zhou, Qi-lin, et al,


Synthesis of 9,9’-Spirobifluorene-1,1’-diol Reduction of Ketones

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


Synthesis of sdp ligands
Synthesis of SDP Ligands Reduction of Ketones

Zhou, Qi-Lin, et al, J. Am.Chem.Soc., 2003, 4404.


Zhou, Q.-L. Reduction of Ketones 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.

Zhou, Qi-Lin, et al, Angew. Chem. Int. Ed., 2005, 1118.



Synthesis of chiral spiro phosphine oxazoline ligands
Synthesis of Chiral Spiro Phosphine-Oxazoline Ligands Reduction of Ketones

Zhou, Q.-L. et al, J. Am.Chem. Soc. 2006, 128, 12886.


Applications asymmetric hydrogenation
Applications: Asymmetric Hydrogenation Reduction of Ketones

Zhou, Q.-L. et al, J. Am. Chem. Soc. 2006, 128, 11774

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%)


Highly enantioselective and diastereoselective synthesis of chiral amino alcohols
Highly Enantioselective and Diastereoselective Synthesis of Chiral Amino Alcohols

Zhou, Qi-Lin, et al, J. Am. Chem. Soc., 2010, 4222.


Enantioselective hydrogenation of arylmethylene cycloalkanones
Enantioselective Hydrogenation of Chiral Amino Alcoholsα-Arylmethylene Cycloalkanones

the asymmetric hydrogenation of exocyclic

α,β-unsaturated ketones is a challenge task

Zhou, Qi-Lin, et al, J. Am. Chem. Soc., 2010, 4538.


Applications: Asymmetric Hydrogenation Chiral Amino Alcohols

Zhou, Q.-L. et al, J. Am. Chem. Soc. 2007, 129, 1868

aldehydes

the first example of asymmetric hydrogenation of aldehyde via DKR


Applications: Asymmetric Hydrogenation Chiral Amino Alcohols

Zhou, Q.-L. et al, Angew. Chem. Int.Ed. 2005, 1118

α,β-unsaturated carboxylic acid

these results are comparable to, or better than,

those obtained with [Ru(OAc)2(binap)] and other catalysts


Applications: Asymmetric Hydrogenation Chiral Amino Alcohols

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


Applications: Asymmetric Hydrogenation Chiral Amino Alcohols

Zhou, Q.-L. et al, Adv. Synth, Catal. 2006, 1271

α,β-unsaturated carboxylic acid


Hydrogenations with chiral spiro phosphine oxazoline ligands
Hydrogenations with Chiral Spiro Phosphine-Oxazoline Ligands Chiral Amino Alcohols

Zhou, Q.-L. et al, J. Am. Chem. Soc. 2008, 130, 8584.

Zhou, Q.-L. et al, J. Am. Chem. Soc. 2010, 132, 1172.

Zhou, Q.-L. et al, J. Am. Chem. Soc. 2006, 128, 12886.


Applications: Asymmetric Hydrogenation Chiral Amino Alcohols

enamines


Applications: Asymmetric Hydrogenation Chiral Amino Alcohols

Zhou, Q.-L. et al, J. Am. Chem. Soc. 2006, 128, 11774

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


Iridium catalyzed asymmetric hydrogenation of cyclic enamines
Iridium-Catalyzed Asymmetric Hydrogenation of Cyclic Enamines

Zhou, Qi-Lin, et al, J. Am. Chem. Soc., 2010, 1366.


Enantioselective iron catalysed o h bond insertions
Enantioselective Iron-catalysed O–H Bond Insertions Enamines

Zhou, Qi-Lin, et al, Natural Chemistry, 2010, 546.


Other developments
Other Developments Enamines

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


Other developments1
Other Developments Enamines

Zhou, Qi-Lin, et al, Angew. Chem. Int. Ed., 2008, 8496.

Copper-Catalyzed Highly Enantioselective Carbenoid Insertion into Si-H Bonds

Zhou, Qi-Lin, et al, Angew. Chem. Int. Ed., 2008, 4351.

Enantioselective Rhodium-Catalyzed Addition of Arylboronic Acids to β-Ketoesters



Ni catalyzed reactions
Ni Catalyzed Reactions Enamines

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


Asymmetric hydrovinylat ion of vinylarenes
Asymmetric hydrovinylat-ion of Vinylarenes Enamines

Zhou, Q.-L. et al, J. Am. Chem. Soc. 2006, 128, 2780


Pd catalyzed carboamination reactions
Pd Catalyzed Carboamination Reactions Enamines

John, Wolfe, et al, J. Am. Chem. Soc. 2010, 12157.


Possible works
Possible Works Enamines


Thanks Enamines


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