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Dendritic Effects in Homogeneous Asymmetric Catalysis

Mitsui, Kazuhiko
http://rave.ohiolink.edu/etdc/view?acc_num=osu1245200227

Abstract Details

2009, Doctor of Philosophy, Ohio State University, Chemistry.
Studies on chiral prolinamide-terminated dendrons and dendrimers for their catalytic and chiroptical properties were undertaken. During the course of this research, a convenient multigram preparation of 4-chloropyridine-2,6-dicarbonyl dichloride was developed. This material was utilized in constructing intramolecularly folded pyridine-2,6-dicarboxamide-based dendrons and dendrimers with chiral prolinamide termini. The design of these supramolecular catalysts was based on concepts of preorganization and cooperativity, which stems from the interworking of natural enzymes. The chiral dendron catalysts were synthesized up to their 3rd generation and tested for their catalytic properties in asymmetric direct aldol reactions. Some selected catalysis experiments showed positive dendritic effects in terms of enantioselectivity and diastereoselectivity. In addition, structurally modified dendron catalysts using the 1,3-isophthalamide branching unit as well as 1st generation dendrimer catalysts were prepared. These catalysts also exhibited notable positive dendrimer effects. Circular dichroism (CD) spectroscopic data on benzyl amine derivatives of these dendrons and dendrimers indicated the presence of a generation-dependent helical bias. The helical conformation was determined to be P from the CD analysis together with computational CD investigations conducted in collaboration with the Hadad research group. Crystal structure of 1st and 2nd generation dendrons confirmed the syn-syn conformations of pyridine-2,6-dicarboxamide focal point as well as the P helical arrangement of the terminal prolinamide dendron for G1.
Jon Parquette, Ph.D. (Advisor)
Thaliyil RajanBabu, Ph.D. (Committee Member)
Christopher Hadad, Ph.D. (Committee Member)
381 p.
Chemistry
Dendritic effect; Dendrimer; Catalysis; Prolinamide; Aldol; Organocatalytic; Circular Dichroism; DFT

Recommended Citations

Citations

  • Mitsui, K. (2009). Dendritic Effects in Homogeneous Asymmetric Catalysis [Doctoral dissertation, Ohio State University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=osu1245200227

    APA Style (7th edition)

  • Mitsui, Kazuhiko. Dendritic Effects in Homogeneous Asymmetric Catalysis. 2009. Ohio State University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=osu1245200227.

    MLA Style (8th edition)

  • Mitsui, Kazuhiko. "Dendritic Effects in Homogeneous Asymmetric Catalysis." Doctoral dissertation, Ohio State University, 2009. http://rave.ohiolink.edu/etdc/view?acc_num=osu1245200227

    Chicago Manual of Style (17th edition)

osu1245200227
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© 2009, all rights reserved.
This open access ETD is published by The Ohio State University and OhioLINK.