NMSU - Department of Chemisty and Biochemistry

JAMES W. HERNDON

Professor

B.S. Chemistry, University of North Carolina-Greensboro, 1979

M.S. Chemistry, Princeton University, Princeton, NJ, 1980
Ph.D. Chemistry, Princeton University, Princeton, NJ, 1983

Research in the Herndon group focuses on the discovery of new organotransition metal-based processes for use in organic synthesis. Of specific interest are reactions that transform simple starting materials into complex products in a general, predictable, efficient, and stereoselective manner. Most of our present activity involves exploration of the coupling reaction between Fischer carbene complexes and highly conjugated acetylene derivatives. Several useful processes have been identified from these studies, and two of the systems under study are detailed below.

The coupling of Fischer carbene complexes with enyne-aldehydes results in furan derivatives (eq 1). The unstable isobenzofuran ring system can be generated using benzo analogs (eq 2). Although unstable, this ring system very predictably undergoes Diels-Alder reactions. This reaction sequence serves as the cornerstone for preparation of pharmaceutically important structures (e.g. the estrogen-like structure depicted in eq 3) from two relatively simple components.

The coupling of Fischer carbene complexes with dienynes results in the synthesis of the benzofuran ring system (eq 4). This process has been found to be very and general and tolerant of a variety of substitution patterns. Numerous medicinally important compounds contain the benzofuran ring system and current research activity involves the synthesis of biologically active compounds for medicinal evaluation.

SELECTED PUBLICATIONS:

“Coupling of N-heterocycle-fused enyne aldehydes with g,d-unsaturated Fischer carbene complexes.”

Zhang, J.; Zhang, Y.; Schnatter, W. F. K.; Herndon, J. W.

Organometallics 2006, 25, ASAP Article.

“Coupling of Fischer Carbene Complexes with Alkynylstyrene Oxides: Synthesis of Benzoxepinones in Competition with Internal Oxygen Atom Transfer.”

Zhang, L.; Herndon, J.W.

Heterocycles 2006, 67, 233-246.

“Reaction Types and Mechanisms: Metathesis Reactions.”

Herndon, J.W.

In Comprehensive Organometallic Chemistry, 3^rd Edition, Eaborn, C. Ed. Elsevier: Oxford, 2005, In Press

“Reaction of Cyclopropylcarbene-Metal Complexes with Nucleophiles, Halogens and HX.”

Reid, M.D.; Tirado, L.; Zhang, J.; Nwamara, D.; Herndon, J.W.

J. Organomet. Chem. 2005,690, 5759-5776.

“Synthesis of hydrophenanthrenes through a “green” Fischer carbene-alkyne coupling process.”

Li, R.; Zhang, L.; Camacho-Davila, A.; Herndon, J.W.

Tetrahedron Lett. 2005, 46, 5117-5120.

“Tandem Isobenzofuran Formation-Diels Alder Reactions in the Coupling of Carbene Complexes with 2-Alkynylbenzaldehyde Derivatives Featuring an Alkyne-Dienophile Tether.”

Luo, Y.; Herndon, J. W.

Organometallics 2005, 24, 3099-3103.

“Annual Survey of the Carbon-Transition Metal Double and Triple Bond for the Year 2003.”

Herndon, J.W.

Coord. Chem. Rev. 2005, 249, 999-1083.

“Synthesis of furan-bridged 10-membered rings through [8+2]-cycloaddition of dienylfurans and acetylenic esters.”

Zhang, L.; Wang, Y.; Buckingham, C.; Herndon, J.W.

Org. Lett. 2005, 7, 1665-1667.

“Benzannulation of heterocyclic ring systems through coupling of Fischer carbene complexes and heterocycle-bridged enynes.”

Zhang, Y.; Candelaria, D.; Herndon, J.W.

Tetrahedron Lett. 2005, 46, 2211-2214.

“Coupling of Propargylsilanes with Fischer Carbene Chromium Complexes: A New Synthesis of Conjugated Dienes.”

Patel, P.; Zhu, Y.; Zhang, L.; Herndon, J.W.

J. Organomet. Chem. 2004, 689, 3379-3387.

“Synthesis of Indanes through Coupling of Ethynylstyrene Derivatives with Carbene Complexes.”

Zhang, L.; Herndon, J.W.

Organometallics 2004, 23, 1231-1235.

“Annual Survey of the Carbon-Transition Metal Double and Triple Bond for the Year 2002.”

Herndon, J.W.

Coord. Chem. Rev. 2004, 248, 3-79.

Annual Survey of the Carbon-Transition Metal Double and Triple Bond for the Year 2001
Herndon, J.W.Coord. Chem. Rev. 2003, 227, Manuscript in Preparation.

Synthesis of furanophane derivatives through [8+2]-cycloaddition of dienylisobenzofuransalkyn and alkynesLuo,

Y.; Herndon, J.W.; Cervantes-Lee, F.
J. Am. Chem. Soc. 2003, 125, In Press

Coupling of Fischer carbene complexes with o-alkynylbenzamides
Ghorai, B.K.; Herndon, J.W.
Organometallics 2003, 22, 3951-3957

Synthesis of Pyrroles through Coupling of Enyne Hydrazones with Fischer Carbene Complexes
Zhang, Y.; Herndon, J.W.
Org. Lett. 2003, 5, 2043-2045

Synthesis of Benzofurans through Coupling of Dienylacetylenes with Carbene Complexes: Total Synthesis of Egonol
Zhang, J.; Zhang, Y.; Zhang, Y.; Herndon, J.W.
Tetrahedron 2003, 63, 5609-5616

Design of New Reaction Processes based on Cyclopropylcarbene Complexes
Herndon, J.W.
Current Organic Chemistry, 2003, 7, 329-352.

Cross Metathesis Reactions using g,d-unsaturated Chromium Carbene Complexes.
Zhang, L.; Herndon, J.W.
Tetrahedron Lett. 2002, 43, 4471-4473.

Inversion of the direction of stereoinduction in the coupling of chiral g,d-unsaturated Fischer carbene complexes with o-ethynylbenzaldehyde.
Ghorai, B.K.; Menon, S.; Johnson, D.L.; Herndon, J.W.
Org. Lett. 2002, 4, 2121-2124.

Synthesis of Furano[2,3-c]-pyran-3-one and Thieno[2,3-c]-pyran-3-one Derivatives through the Coupling of 3-Alkynyl-2-heteroaromatic Carboxaldehydes with Fischer Carbene Complexes; Total Synthesis of a Baccharis-derived Cadinene Derivative.
Zhang, Y.; Herndon, J.W.
J. Org. Chem. 2002, 67. 4177-4185.

Annual Survey of Carbon-Transition Metal Double and Triple Bond for the Year 2000
Herndon, J.W.
Coord. Chem. Rev. 2002, 227, 1-58.

One-Step Convergent Synthesis of the Steroid Ring System via the Coupling of g,d-unsaturated Fischer Carbene Complexes with o-ethynylbenzaldehyde.
Ghorai, B.K.; Herndon, J.W.
Organic Letters 2001, 3, 3535-3538.

Palladium-catalyzed aminobenzannulation during Sonogashira couplings using o-bromoacetophenone.
Herndon, J.W.; Zhang, Y.; Wang, K.
J. Organometal. Chem. 2001, 634, 1-4.

Ring Expansion in the Coupling of Fischer-Carbene Complexes with 1-Alkynyl-1-Hydroxy Cyclic Compounds.
Zora, M.; Herndon, J.W.; Li, Y.; Rossi, J.
Tetrahedron 2001, 61, 5097-5107.

Annulation Selectivity in the Coupling of Fischer Carbene Complexes with o-Alkylbiphenyl and o-Alkynylstyrene Derivatives.
Jackson, T.J.; Herndon, J.W.
Tetrahedron 2001, 61, 3859-3868.

Annual Survey of Carbon-Transition Metal Double and Triple Bond for the Year 1999
Herndon, J.W.
Coord. Chem. Rev. 2001, 214, 215-285.

Synthesis of Furanopyrone and Thiophenopyrone Derivatives through the Coupling of 3-Alkynyl-2-heteroaromatic Carboxaldehydes with Fischer Carbene Complexes.
Zhang, Y.; Herndon, J.W.
Tetrahedron Lett. 2001, 42, 777-779.

Synthesis of Benzofuran Derivatives through the Coupling of Conjugated Dienynes with Fischer Carbene Complexes.
Herndon, J.W.; Zhang, Y.; Wang, H.; Wang, K.
Tetrahedron Lett. 2000, 41, 8687-8690.

Generation and Trapping of Isobenzofuran Intermediates formed in the Coupling of Fischer Carbene Complexes and ortho-Alkynylbenzoyl Derivatives.
Jiang, D.; Herndon, J.W.
Organic Letters 2000, 2, 1267-1269.

Synthesis of Alkylidenecyclopentenones and Dialkylidenecyclopentenones via the Coupling of Propargylic Alcohol and 2-Alkyne-1,4-diol Derivatives with Cyclopropylcarbene-Chromium Complexes.
Herndon, J.W., Zhu, J.; Sampedro, D.
Tetrahedron 2000, 60, 4985-4993.

Selective Remote Functionalization of Alkyl Side Chains in the Coupling of Fischer Carbene Complexes with Conjugated Enediynes
Zhang, Y., Herndon, J.W.
Tetrahedron 2000, 60, 2175-2184.

Advances in Strained and Interesting Organic Molecules. Volume 8.
Herndon, J.W. Book Review for:
J. Am. Chem. Soc. 2000, 122, 11570.

Introduction to a Special Edition of Tetrahedron entitled: Carbene Complexes in Organic Chemistry.
Herndon, J.W.
Tetrahedon 2000, 60, R9-R9.

The Use of Fischer Carbene Complexes for the Preparation of Five-Membered Carbocyclic Rings.
Herndon, J.W.
Tetrahedron 2000, 60, 1257-1280.

Annual Survey of Carbon-Transition Metal Double and Triple Bond for the Year 1998
Herndon, J.W.
Coord. Chem. Rev. 2000, 209, 387-451.

Applications of Carbene Complexes Directed Toward Organic Synthesis
Herndon, J.W.
Coord. Chem. Rev. 2000, 206-207, 237-262.

Recent Presentations:

Synthesis of benzofurans through the coupling of highly conjugated acetylenes and carbene complexes
Herndon JW, Saavedra R,
Abstracts of Papers of The American Chemical Society, v. 223(pt. 1) PP. U289-U289 Apr 7, 2002.

Synthesis of isoquinolines and benzophenanthridines through the coupling of beta-cyanoarbene complexes with O-alkynylbenzadehyde derivatives
Herndon JW, Jiang DL, Ghorai BK,
Abstracts of Papers of The American Chemical Society, v. 223(pt. 2) pp. B192-B192, Apr 7, 2002.