Methyl 4‐Hydroxy‐5‐iodo‐2,3‐dimethoxy‐6‐methylbenzoate: The Aromatic Fragment of Calichemicin γ. Synthesis, X‐Ray Crystallographic Analysis, and Properties

Nicolaou, K. C.; Ebata, Takuma; Stylianides, N. A.; Groneberg, Robert D.; Carrol, P. J.

doi:10.1002/anie.198810971

Cited by 31 publications

(6 citation statements)

References 11 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

Section: Highlights Of Contributions From the Author’s Laboratoriesmentioning

confidence: 99%

“…Along the way we were delighted and fascinated in equal measure by the many twists, turns, and facets of the synthesis and the technologies developed during its course. These aspects of the project included the unusual resolution 41 of the aromatic fragment of calicheamicin g 1 I and the use of the Ramberg-Ba¨cklund reaction for the preparation of enediynes. 42 Most importantly, calicheamicin g 1 I gifted us with the opportunity to explore the chemistry and biology of the enediynes as a tunable class of compounds that could be used to cleave DNA and kill tumor cells.…”

mentioning

confidence: 99%

See 1 more Smart Citation

Constructing molecular complexity and diversity: total synthesis of natural products of biological and medicinal importance

et al. 2012

Self Cite

View full text Add to dashboard Cite

The advent of organic synthesis and the understanding of the molecule as they occurred in the nineteenth century and were refined in the twentieth century constitute two of the most profound scientific developments of all time. These discoveries set in motion a revolution that shaped the landscape of the molecular sciences and changed the world. Organic synthesis played a major role in this revolution through its ability to construct the molecules of the living world and others like them whose primary element is carbon. Although the early beginnings of organic synthesis came about serendipitously, organic chemists quickly recognized its potential and moved decisively to advance and exploit it in myriad ways for the benefit of mankind. Indeed, from the early days of the synthesis of urea and the construction of the first carbon-carbon bond, the art of organic synthesis improved to impressively high levels of sophistication. Through its practice, today chemists can synthesize organic molecules—natural and designed—of all types of structural motifs and for all intents and purposes. The endeavor of constructing natural products—the organic molecules of nature—is justly called both a creative art and an exact science. Often called simply total synthesis, the replication of nature’s molecules in the laboratory reflects and symbolizes the state of the art of synthesis in general. In the last few decades a surge in total synthesis endeavors around the world led to a remarkable collection of achievements that covers a wide ranging landscape of molecular complexity and diversity. In this article, we present highlights of some of our contributions in the field of total synthesis of natural products of biological and medicinal importance. For perspective, we also provide a listing of selected examples of additional natural products synthesized in other laboratories around the world over the last few years.

show abstract

Section: Highlights Of Contributions From the Author’s Laboratoriesmentioning

confidence: 99%

mentioning

confidence: 99%

Constructing molecular complexity and diversity: total synthesis of natural products of biological and medicinal importance

et al. 2012

Self Cite

View full text Add to dashboard Cite

show abstract

“…40 Also quite interesting was the observation, by X-ray crystallography, of two forms of crystals of the fully substituted aromatic moiety of calicheamicin γ 1 I (Figure 17), each containing enantiomeric molecules of unusual shapes [(R,R,R) and (S,S,S)]. 41 In 1994, Samuel J. Danishefsky and his team published their elegant total synthesis of calicheamicin γ 1…”

Section: Calicheamicin γ 1 Imentioning

confidence: 99%

“…FIGURE 17. Spontaneous resolution of a calicheamicin γ 1 I aromatic fragment into crystals containing enantiomers [(R,R,R) and (S,S,S)] (Nicolaouet al, 1988) 41. …”

mentioning

confidence: 99%

Inspirations, Discoveries, and Future Perspectives in Total Synthesis

Nicolaou

2009

J. Org. Chem.

Self Cite

View full text Add to dashboard Cite

The last one hundred years have witnessed a dramatic increase in the power and reach of total synthesis. The pantheon of accomplishments in the field includes the total synthesis of molecules of unimaginable beauty and diversity such as the four discussed in this article: endiandric acids (1982), calicheamicin γ 1 I (1992), Taxol ® (1994), and brevetoxin B (1995). Chosen from the collection of the molecules synthesized in the author's laboratories, these structures are but a small fraction of the myriad constructed in laboratories around the world over the last century. Their stories, and the background on which they were based, should serve to trace the evolution of the art of chemical synthesis to its present sharp condition, an emergence that occurred as a result of new theories and mechanistic insights, new reactions, new reagents and catalysts, and new synthetic technologies and strategies. Indeed, the advent of chemical synthesis as a whole must be considered as one of the most influential developments of the twentieth century in terms of its impact on society.

show abstract

“…These rewards included a stereospecific 3,3-sigmatropic rearrangement employed to install the sulfur atom on one of the molecule's carbohydrate units (Figure 8a), the stereoselective construction of the novel NH-O glycoside bond (Figure 8b), the use of the Ramberg-Ba ¨cklund reaction for the preparation of enediynes (Figure 8c) and the casting of calicheamicin's signature structural motif, its enediyne system, followed by a neighboring groupassisted inversion of stereochemistry through a novel lactonization (Figure 8d). Additionally, the spontaneous conglomerate resolution of calicheamicin's fully substituted aromatic moiety in two enantiomeric forms (Figure 8e), 31 structurally determined by X-ray crystallographic techniques, was both surprising and reminiscent of Pasteur's resolution of tartaric acid. Other important spin-offs from this project included the synthesis and study of designed enediynes and oligosaccharides, whose chemical and biological properties were extremely revealing.…”

Section: Introductionmentioning

confidence: 99%

Joys of Molecules. 1. Campaigns in Total Synthesis

Nicolaou

2005

J. Org. Chem.

Self Cite

View full text Add to dashboard Cite

Our bodies are made of molecules, and it is from molecules that we derive our strength and joys. The joys of molecules manifest themselves in many ways. These include beautiful colors, exquisite aromas, distinct tastes, psychological ups and downs, and intellectual inspirations, among other forms of stimulation, material or spiritual. In this Perspective, written on the occasion of the 2005 American Chemical Society Arthur C. Cope Award address, I recount some of the joys I have experienced and shared with my students during campaigns to synthesize some of Nature's most intriguing and complex molecules.

show abstract

Methyl 4‐Hydroxy‐5‐iodo‐2,3‐dimethoxy‐6‐methylbenzoate: The Aromatic Fragment of Calichemicin γ. Synthesis, X‐Ray Crystallographic Analysis, and Properties

Cited by 31 publications

References 11 publications

Constructing molecular complexity and diversity: total synthesis of natural products of biological and medicinal importance

Constructing molecular complexity and diversity: total synthesis of natural products of biological and medicinal importance

Inspirations, Discoveries, and Future Perspectives in Total Synthesis

Joys of Molecules. 1. Campaigns in Total Synthesis

Contact Info

Product

Resources

About