Chemistry 842 - Fall 2004
Main Group Organometallic Chemistry
Instructor: Hans J. Reich, 6311 Chemistry, Tel: 262-5794, email: reich@chem.wisc.edu
Main Group Organometallic Chemistry is offered approximately every third spring semester.
Content: This course will cover selected preparative, structural, stereochemical,
mechanistic and spectroscopic aspects of main group organometallic compounds, as well as
their application to solving problems in organic synthesis. The principal elements covered will
be lithium, boron, silicon, tin, sulfur and selenium, but essential features of the chemistry of a number
of other main group elements, and chemistry of transition metals (such a copper, palladium and zinc) where it intersects with main group chemistry will also be addressed.
Prerequisites: Chemistry 841 recommended or consent of instructor.
Time and Place: MWF, 9:55 AM, Room 1315, Chemistry
Grading: Each student registered for credit is required to prepare either a report on an
aspect of the course relevant to his or her research, or a research proposal in an area relevant
to course material.
Chemistry 842 - Fall 2004 Course Outline
- Main Group Organometallic Chemistry - Some Generalities
- Organolithium Chemistry
- Methods for preparing organolithium reagents: reduction of C-X bonds, Li/H exchange (metalation), Li/M exchange (M = Br, I, Sn, Hg, Se, Te), Shapiro reaction, addition to multiple bonds
- Structure and dynamics in solids and solution - aggregation, ion pair structure
- Stereochemistry of organolithium reagents
- Synthetic applications of organolithium reagents
- Organocopper and Organozinc Chemistry
- Preparation and structure
- Typical reactions
- Asymmetric synthesis using Zn and Cu reagents
- Organotin and Organosilicon Chemistry
- Comparison of C, Si, Ge and Sn
- Preparation of organosilicon compounds and reagents
- Electrophilic and nucleophilic cleavage of C-Si bonds (Peterson, Brook)
- Preparation and uses of tin reagents (R3SnH, R3SnLi, R3SnSnR3, etc)
- Formation of C-Sn bonds
- Electrophilic, nucleophilic and radical substitution of C-Sn bonds, stereochemistry
- Organoboron, Organoaluminum, Organoindium
- Preparation of organoboranes
- Typical reactions of organoboranes
- Organoaluminum chemistry
- Organoindium chemistry
- Organosulfur and Organoselenium Chemistry
- Comparison of S/Se/Te
- Sulfur and Selenium reagents (PhSeX, PhSeSePh, PhSeM, etc)
- Sulfoxide and Selenoxide eliminations
- Lithio sulfides and selenides
- Phosphorus, Arsenic, Antimony, Bismuth
- The Halogens, and Others