Inventing chemical reactions for new syn-theses using organometallic complexes and the design of new biodegradable polymers
based on polylactic acids is the focus of our
research. In addition to basic training in
synthesis and polymer chemistry, students
in my group develop expertise in the gamut
of modern analytical methods for molecu-
lar and macromolecular characterization
and are exposed to
a broad range of sci-
ence through exten-
with other groups on
campus. Overviews of
two current projects
are given below.
The first project involves transition metal
chemistry of boron. We began our research
in this area with hopes of exploring the fun-
damental chemistry of metal boryl complex-
es (M–BX2) and examining reactions of bo-
ron-element bonds with unsaturated organic
ligands coordinated to metal centers. In the
course of this work, we discovered unusual
selectivities for olefin borylation reactions
and were able to control catalytic chemis-
try by tuning the ligands attached to boron.
Most recently, we reported the first example
of catalytic synthesis of a B–C bond from an
arene C–H bond and a borane B–H bond. This
marked a significant advance in catalytic hy-
drocarbon functionalization, which has been
one of chemistry’s “Holy Grails”. In addition,
the sterically dictated regioselectivities in
these reactions provide the first general solu-
tions to long-standing problems in aromatic
substitution chemistry. In the future, we plan
to explore issues that dictate selectivity in
The second research area involves the synthe-
sis of biodegradable and biorenewable poly-
mers through ring-opening polymerization
reactions. These are important materials that
provide environmentally friendly alternatives
to petroleum-based polymers. We present-
ly are designing polylactic acid copolymers
that can be tailored for applications in tissue
regeneration and drug delivery. This project
has spawned a collaboration studying bone
growth with the Department of Physiology.
Bone forming cells (osteoblasts) grown
on a “tailored” PLA copolymer.
California Institute of Technology;
Univ. of Chicago;
Postdoctoral Fellow, 1990-92,
Univ. of California, Berkeley.
Milton R. (Mitch) Smith
C–H Activation/Borylation/Oxidation: A
One-Pot Unified Route to Meta-Substituted
Phelols Bearing Ortho-/Para-Directing
Groups, R. E. Maleczka Jr., F. Shi, D. Holmes,
M.R. Smith III, J. Am. Chem. Soc. 2003, 125,
Remarkably Selective Iridium Catalysts for
Elaboration of C–H Bonds, J.-Y. Cho, M. K.
Tse, D. Holmes, R. E. Maleczka Jr., M. R.
Smith III, Science 2002, 295, 305.
Steric and Chelate Directing Effects in
Aromatic Borylation, J.-Y. Cho, C. N. Iverson,
M. R. Smith III, J. Am. Chem. Soc. 2001,
Stereoselective Polymerization of a
Racemic Monomer with a Racemic Catalyst:
Direct Preparation of the Polylactic Acid
Stereocomplex from Racemic Lactide, C. P.
Radano, G. L. Baker, M. R. Smith III, J. Am.
Chem. Soc. 2000, 122, 1552.
Stoichiometric and Catalytic B–C Bond
Formation from Unactivated Hydrocarbons
and Boranes, C. N. Iverson, M. R. Smith III,
J. Am. Chem. Soc. 1999, 121, 7696.