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Hydrozirconation/Zr-Zn Transmetalation/Aldimine Addition: One-Pot Synthesis of Allylic, C-Cyclopropylalkyl, and Homoallylic Amines from Alkynes

Kendall, Christopher (2005) Hydrozirconation/Zr-Zn Transmetalation/Aldimine Addition: One-Pot Synthesis of Allylic, C-Cyclopropylalkyl, and Homoallylic Amines from Alkynes. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

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Abstract

The Zr-Zn transmetalation, aldehyde addition methodology developed in the Wipf group was extended to the synthesis of allylic amines. The use of toluene as a reaction solvent was required to obtain high yields and low reaction times. N-Phosphinoyl-, N-sulfonoyl-, and N-carbamoylimines were excellent substrates for this transformation. Many chiral ligands were tested for asymmetric catalysis, but minimal ee was achieved. Addition to chiral phosphinimines was also attempted, but the diastereoselectivities were low.A novel three-component C-cyclopropylalkylamine synthesis was discovered while attempting to perform the allylic amine synthesis in CH2Cl2. The mechanism of this transformation is not fully understood; however, this is the first reported example of a high-yielding Simmons-Smith cyclopropanation with CH2Cl2 as the carbene precursor. This reaction was optimized by adding CH2I2 to the reaction mixture once all imine was consumed. Addition of CH2I2 prior to imine substrate resulted in homoallylic amine formation.


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Details

Item Type: University of Pittsburgh ETD
Status: Unpublished
Creators/Authors:
CreatorsEmailPitt UsernameORCID
Kendall, Christopherchristopher.kendall@umontreal.ca
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairWipf, Peterpwipf@pitt.eduPWIPF
Committee MemberDay, Billybday@pitt.eduBDAY
Committee MemberCurran, Denniscurran@pitt.eduCURRAN
Committee MemberNelson, Scottsgnelson@pitt.eduSGNELSON
Date: 31 January 2005
Date Type: Completion
Defense Date: 20 October 2004
Approval Date: 31 January 2005
Submission Date: 22 October 2004
Access Restriction: No restriction; Release the ETD for access worldwide immediately.
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: Allylic Amines; Imine Addition; Organic Chemistry; Organometallic Chemistry; Homoallylic Amines; Simmons-Smith Cyclopropanation
Other ID: http://etd.library.pitt.edu/ETD/available/etd-10222004-022505/, etd-10222004-022505
Date Deposited: 10 Nov 2011 20:03
Last Modified: 15 Nov 2016 13:50
URI: http://d-scholarship.pitt.edu/id/eprint/9501

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