Cluster Preface: Modern Boron Chemistry: 60 Years of the ­Matteson Reaction

We are thrilled to present this Special Issue of SYNLETT to commemorate the 60th anniversary of Professor Donald Matteson’s publication entitled ‘Neighboring Boron in ­Nucleophilic Displacement’.¹ This seminal report describes the discovery of the 1,2-boronate rearrangement reaction. Prof. Matteson is currently emeritus Professor of Chemistry at Washington State University in Pullman, WA. It was in his laboratories there that a wealth of organoboron chemistry was discovered, including the work that inspires this Special Issue. Prof. Matteson completed his bachelor’s degree under the tutelage of Henry Rapoport at UC Berkeley in 1954 and his Ph.D. in 1957 with Harold R. Snyder at the University of Illinois at Urbana-Champaign. In 1958, after a short appointment at the du Pont Central Research and Development Laboratories, he joined the faculty at Washington State University. Over the course of his career, he has authored >200 publications that have shaped the field of organoboron chemistry. While Prof. Matteson’s publication back in 1963 is not his most cited work, this publication clearly has inspired the development of numerous new synthetic methods and it continues to inspire many scientists in our community today.

To give the 1963 discovery of the Matteson rearrangement some context, it was discovered at a time when new carbonyl compounds were most often characterized by elemental analysis of their hydrazone derivatives, when starting annual salaries for an assistant professor were $5700,² and when analysis of compounds by state-of-the-art 60 MHz NMR might require collaboration with Varian. The discovery of the 1,2-boronate rearrangement was enabled by the recently developed (1957) synthesis of vinylmagnesium bromide by Normant,³ which provided access to vinylboronic esters. In 1959, Matteson employed the latter compounds in an atom-transfer radical addition reaction to furnish the first α-bromoboronic ester 1 (Scheme 1).⁴ While Mikhailov had shown that β-bromo organoboranes undergo elimination in the presence of nucleophiles,⁵ and ­Hawthorne had shown that γ-bromo organoboranes ring-close to cyclopropanes,⁶ the reactivity of α-bromo organo­boranes was uncharted territory. As Prof. Matteson himself describes,⁷ “With a very naive idea of what might be done with the product (1), I suggested to Raymond Mah, my first graduate student, that he phenylate the boron atom with the Grignard reagent…”. They found that α-bromo boronic ester 1 was converted into the substitution product 3, presumably through the intermediacy of four-coordinate borate 2, a proposal that was supported by the reaction between 4 and sodium butoxide to furnish 3. The conversion of boron ‘ate’ complex 2 into boronic ester 3 was proposed to occur through a transition state represented by 7 in the original paper.¹ As they say, “The rest is history.” The involvement of 7 suggested a reaction that is stereospecific with respect to both the migrating group (X) and the electrophilic carbon atom. These features would later be verified, and they continue to be employed in the development of important strategies for asymmetric synthesis. In addition, with appropriate reaction design, strategies that employ ensembles such as 7 for asymmetric catalysis also continue to emerge.

Scheme 1

While much has changed in the field of chemistry since the process in Scheme 1 was elucidated 60 years ago, that the inner workings of the Matteson rearrangement continue to be employed in creative new ways points to the impact of this fundamental reaction. As you read through the collection of invited articles in this Special Issue, we hope that you too will be inspired to employ 1,2-boronate rearrangements in innovative ways or be captivated by other exciting new directions in boron chemistry reported herein.

James P. Morken

Varinder Aggarwal

October 2023

• References

• 1 Matteson DS. J. Am. Chem. Soc. 1963; 85: 2599
• 2 Hansen D. After 50 years, chemist still loves a good interaction. The Spokesman-Review. Spokane Washington Dec 16 2008
• 3 Normant H. Bull. Soc. Chim. Fr. 1957; 728
• 4 Matteson DS. J. Am. Chem. Soc. 1959; 81: 5004
• 5 Mikhailov BM, Aronovich PM. Russ. Chem. Bull. 1961; 10: 860
• 6 Hawthorne MF. J. Am. Chem. Soc. 1960; 82: 1886
• 7 Matteson DS. Unstable Intermediates as Keys to Synthesis with Organoboron Compounds . In Borong Reagents in Synthesis, Coca, A., Ed.: ACS Symposium Series 1236; American Chemical Society, Washington DC, 2016, Chap. 5, 173.