Carbon atom insertion: an efficient synthesis of ishwarane1

Cory, Robert M.; McLaren, Fred R.

doi:10.1039/c39770000587

Cited by 23 publications

(12 citation statements)

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“…In their 1977 synthesis of ishwarane (21), Cory and McLaren introduced the unique idea of ''carbon atom insertion'' in one of the most striking examples of the power of C-H activation in total synthesis (Scheme 6). 25 It also served as an early demonstration of the facility in which carbenes can directly insert into unactivated C-H bonds. The protocol begins with the simple bicycle 18 being treated with dibromocarbene generated in situ to diastereoselectively cyclopropanate one face of the olefin, giving intermediate 19.…”

Section: Ishwarane-1977-corymentioning

confidence: 99%

C–H functionalization logic in total synthesis

2011

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In this critical review, the strategic and economic benefits of C-H functionalization logic will be analyzed through the critical lens of total synthesis. In order to illustrate the dramatically simplifying effects this type of logic can potentially have on synthetic planning, we take the reader through a series of case studies in which it has already been successfully applied. In the first section, a chronological look at key historical syntheses will be examined, leading into modern day examples. In the second section, our own experience with applying and executing synthesis with a C-H functionalization "mindset" will be discussed (114 references).

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Section: Ishwarane-1977-corymentioning

confidence: 99%

C–H functionalization logic in total synthesis

2011

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“…The product formed was identified as 7,7-dichlorobicyclo[4.1.0]heptane ( 17 ) and its formation was attributed to the generation of dichlorocarbene ( 15 ) via base-mediated α-elimination. Several years later, Cory and McLaren showcased the enormous potential of this method during their total synthesis of ishwarane ( 21 ). Olefin 18 was treated with tetrabromomethane and an excess of methyllithium at −78 °C, mediating the formation of dibromocyclopropane 19 .…”

Section: Cyclopropanation Methodsmentioning

confidence: 99%

Cyclopropanation Strategies in Recent Total Syntheses

2017

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Complex molecular architectures containing cyclopropanes present significant challenges for any synthetic chemist. This review aims to highlight the strategic considerations for introduction of the cyclopropane motif in a collection of recent total syntheses. At first, an overview of the most important and widely used cyclopropanation techniques is presented, followed by a discussion of elegant approaches and clever solutions that have been developed to enable the synthesis of various unique cyclopropane natural products or use of cyclopropanes as versatile strategic intermediates.

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“…In 1977, an early contribution of non‐transition‐metal‐catalyzed CH insertion for the synthesis of natural products was reported by Cory et al 143a. When targeting the tetracyclic sesquiterpene ishwarane ( 284 ), they envisioned that CH insertion could occur from cyclopropylcarbene 283 into a specific CH bond (the C9‐position) to form the requisite six‐membered ring (Scheme ).…”

Section: Cc Bond Formationmentioning

confidence: 99%