The Rearrangement of Allyl Groups in Three-Carbon Systems. II<sup>1</sup>

Named organic reactions. As chemists, we're all familiar with them: who can forget the Diels-Alder reaction? But how much do we know about the people behind the names? For example, can you identify a reaction named for a woman? How about a reaction discovered or developed by a woman but named for her male adviser? Our attempts to answer these simple questions started us on the journey that led to this Account. We introduce you to four reactions named for women and nine reactions discovered or developed by women. Using information obtained from the literature and, whenever possible, through interviews with the chemists themselves, their associates, and their advisers, we paint a more detailed picture of these remarkable women and their outstanding accomplishments. Some of the women you meet in this Account include Irma Goldberg, the only woman unambiguously recognized with her own named reaction. Gertrude Maud Robinson, the wife of Robert Robinson, who collaborated with him on several projects including the Piloty-Robinson pyrrole synthesis. Elizabeth Hardy, the Bryn Mawr graduate student who discovered the Cope rearrangement. Dorothee Felix, a critical member of Albert Eschenmoser's research lab for over forty years who helped develop both the Eschenmoser-Claisen rearrangement and the Eschenmoser-Tanabe fragmentation. Jennifer Loebach, the University of Illinois undergraduate who was part of the team in Eric Jacobsen's lab that discovered the Jacobsen-Katsuki epoxidation. Keiko Noda, a graduate student in Tsutomu Katsuki's lab who also played a key role in the development of the Jacobsen-Katsuki epoxidation. Lydia McKinstry, a postdoc in Andrew Myers's lab who helped develop the Myers asymmetric alkylation. Rosa Lockwood, a graduate student at Boston College whose sole publication is the discovery of the Nicholas reaction. Kaori Ando, a successful professor in Japan who helped develop the Roush asymmetric alkylation as a postdoc at MIT. Bianka Tchoubar, a critically important member of the organic chemistry community in France who developed the Tiffeneau-Demjanov rearrangement. The accomplishments of the women in this Account illustrate the key roles women have played in the discovery and development of reactions used daily by organic chemists around the world. These pioneering chemists represent the vanguard of women in the field, and we are confident that many more of the growing number of current and future female organic chemists will be recognized with their own named reactions.

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“…24 Subsequent mechanistic investigations by Hardy proved that the rearrangement occurs over six atoms and is intramolecular (24 to 25). 25…”

Section: Methodsmentioning

confidence: 99%

Critical Perspective: Named Reactions Discovered and Developed by Women

Olson

Shea

2011

Acc. Chem. Res.

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“…T he Cope rearrangement is a [3,3] allylic transposition reaction that proceeds via the concerted cleavage and reformation of C−C bonds. 1 Since its discovery 80 years ago, 2−4 the reaction has found considerable use in the synthesis of complex molecules, 5 including many recent methods and strategies.…”

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confidence: 97%

“…

We report that oxo-or aza-bridged alkylidenemalononitrile-cycloheptenes undergo a [3,3] ring rearrangement to yield cyclopenta-fused dihydro-furans or pyrroles. Described herein are the origins of the serendipitous discovery, scope studies, and representative functional group interconversion chemistry.

…”

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confidence: 99%

“…25,26 Depending on the peripheral 1,5-diene structure, there are oxy-Cope-based ring expansions (Scheme 1A, eq 2) and ring rearrangements (Scheme 1A, eq 3). There are also Claisen [3,3] ring expansions and rearrangements. 30−35 Herein, we report the serendipitous discovery of a new class of 1,5-diene, bicyclo[3.2.1]octene alkylidenemalononitriles I that undergo Cope ring rearrangement to uniquely decorated cis-fused heteroatomic hexahydropentalenes II (Scheme 1B).…”

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confidence: 99%

“…Knowing that the [3,3] ring rearrangement is favored at elevated temperatures, we next examined the scope of the transformation using the ring-closed scaffolds 2a−2g with a focus on key structural requirements for reactivity (Scheme 3). The starting materials (2a−2g) for this study are prepared via an iterative alkylation/Cope rearrangement/ring-closing metathesis sequence, which we recently described.…”

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confidence: 99%

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[3,3] Ring Rearrangement of Oxo- or Aza-Bridged Bicyclo[3.2.1]octene-Based 1,5-Dienes

et al. 2021

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The Alkylation of Esters and Nitriles

2011

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This chapter is concerned with the reactions of metal salts (enolates) of active methylene compounds with alkylating agents such as alkyl halides to produce allyl derivatives. The first example of this reaction is found in the literature when Geuther prepared ethyl alpha‐ethyl acetoacetate by the reaction of the sodium enolate of ethyl acetoacetate with ethyl iodide. The active methylene compounds considered in the chapter include malonic esters, cyanoacetic esters, malonitriles, monocarboxylic esters and mononitriles. These classes of compounds are characterized by the presence of one or more acidic hydrogen atoms attached to carbon. Only C‐alkylation has been observed with active methylene compounds and are discussed here. Several alternative methods for the preparation of alkyl and aryl derivatives of carboxylic esters and nitriles have been included.

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The Rearrangement of Allyl Groups in Three-Carbon Systems. II¹

Cited by 34 publications

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Critical Perspective: Named Reactions Discovered and Developed by Women

Critical Perspective: Named Reactions Discovered and Developed by Women

[3,3] Ring Rearrangement of Oxo- or Aza-Bridged Bicyclo[3.2.1]octene-Based 1,5-Dienes

The Alkylation of Esters and Nitriles

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The Rearrangement of Allyl Groups in Three-Carbon Systems. II1

Cited by 34 publications

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Critical Perspective: Named Reactions Discovered and Developed by Women

Critical Perspective: Named Reactions Discovered and Developed by Women

[3,3] Ring Rearrangement of Oxo- or Aza-Bridged Bicyclo[3.2.1]octene-Based 1,5-Dienes

The Alkylation of Esters and Nitriles

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The Rearrangement of Allyl Groups in Three-Carbon Systems. II¹