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Endeavors in Methodology Development and Natural Product Total Synthesis

Li, Xiben (2014) Endeavors in Methodology Development and Natural Product Total Synthesis. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

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This thesis deals with the development of new reaction methodology, as well as total synthesis of natural products.
Chapter 1 describes readily available rhodium(II) salts catalyzed B-H insertion reactions between NHC-boranes (NHC-BH3) and diazocarbonyl compounds (N2CR1COR2). Stable α-NHC-boryl carbonyl compounds (NHC-BH2-CHR1COR2) are isolated in good yields. The reaction is a reliable way to make boron-carbon bonds with good tolerance for variation in both the NHC-borane and diazocarbonyl components. It presumably occurs by insertion of a transient rhodium carbene into a boron-hydrogen bond of the NHC-borane. Competition experiments show that a typical NHC-borane is highly reactive toward rhodium carbenes.
Chapter 2 describes the synthetic routes towards the synthesis of tulearin A and tulearin C. Large scale synthesis of the bottom fragments (C1-C12) and the top fragment (C13-C26) for tulearin A was accomplished. Different synthetic routes were tested to accomplish the total synthesis of tulearin A. Some major problems toward the total synthesis of tulearin A were identified and solved. Meanwhile a novel synthetic route towards the total synthesis of tulearin C was developed. New methodologies were applied to make the synthesis more efficient. The total synthesis of tulearin C was not accomplished because of the difficulty of removal of the acetate protecting group at C17.


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Item Type: University of Pittsburgh ETD
Status: Unpublished
CreatorsEmailPitt UsernameORCID
Li, Xibenxil64@pitt.eduXIL64
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairCurran, Denniscurran@pitt.eduCURRAN
Committee MemberPaul, Floreancigflorean@pitt.eduFLOREAN
Committee MemberWipf, Peterpwipf@pitt.eduPWIPF
Committee MemberZemaitis, Michaelmaz@pitt.eduMAZ
Date: 29 May 2014
Date Type: Publication
Defense Date: 7 March 2014
Approval Date: 29 May 2014
Submission Date: 24 March 2014
Access Restriction: No restriction; Release the ETD for access worldwide immediately.
Number of Pages: 182
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: Boron-Hydrogen bond insertion, NHC-Boranes, Total synthesis, Tulearins
Date Deposited: 29 May 2014 17:13
Last Modified: 15 Nov 2016 14:18


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