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Stereoselective Synthesis of Spirooxindole Amides and Cyanohydrin Alkyl Ethers

Lu, Chunliang (2014) Stereoselective Synthesis of Spirooxindole Amides and Cyanohydrin Alkyl Ethers. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

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A new family of spirooxindole amides were synthesized by a sequence of hydrozirconation, acylation, and intramolecular cyclization reactions. Three of the four possible diastereomers can be obtained as the major isomers through this process. The spirooxindole structure has many points for diversification, and a 37-membered library was synthesized through this approach by collaborators. A comparison with known compound collections showed that this new spirooxindole library possessed good chemical diversity.

Cyanohydrin alkyl ethers, the key intermediate in the above multi-component hydrozironation reaction, were effectively synthesized through a Brønsted acid-mediated hydrocyanation of vinyl ethers. The enantiomerically enriched product can be obtained by asymmetric hydrocyanation of vinyl ethers catalyzed by a chiral Brønsted acid, and the catalyst
can be regenerated by PhOH. As far as we know, this research represents the first example of chiral Brønsted acid mediated intermolecular addition of silylated nucleophiles with vinyl ethers. The ion pair interaction between the conjugate base of the chiral Brønsted acid and the
oxocarbenium ion was revealed by computational modeling, which explained the origin of the enantioselectivity and the substrate scope of this reaction.


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Item Type: University of Pittsburgh ETD
Status: Unpublished
CreatorsEmailPitt UsernameORCID
Lu, Chunliangchl110@pitt.eduCHL110
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairFloreancig, Paulflorean@pitt.eduFLOREAN
Committee MemberBrummond, Kaykbrummon@pitt.eduKBRUMMON
Committee MemberCohen, Theodorecohen@pitt.eduCOHEN
Committee MemberXie, Xiang-Qunxix15@pitt.eduXIX15
Date: 31 January 2014
Date Type: Publication
Defense Date: 1 October 2013
Approval Date: 31 January 2014
Submission Date: 23 October 2013
Access Restriction: No restriction; Release the ETD for access worldwide immediately.
Number of Pages: 150
Institution: University of Pittsburgh
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Degree: PhD - Doctor of Philosophy
Thesis Type: Doctoral Dissertation
Refereed: Yes
Uncontrolled Keywords: Hydrozirconation, Spirooxindole Amides, Hydrocyanation, Asymmetric Catalysis,Cyanohydrin Alkyl Ethers
Date Deposited: 31 Jan 2014 20:56
Last Modified: 15 Nov 2016 14:15


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