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2-quinuclidonium tetrafluoroborate   

11 June 2006 6,855 views 6 Comments

quinuclidonium.jpg

Stoltz and Tani. Nature, 2006,441 (7094) pp 731 DOI: 10.1038/nature04842

Just a quick postlett (I might trade-mark that…) to point out Stoltz’s total synthesis in Nature, as mentioned by “ddd” in the previous post’s comments. This little beasty has been the burden of much discussion and controversy in the community, and the accompanying X-ray is very interesting. Y’see, it’s an anti-Bredt amide, where the nitrogen LP has been forced out of conjugation from the carbonyl, resulting in a radically different amide chemistry (the N behaves much more like an amine).

quinuclidonium_2.jpg
After a failed synthesis attempt using C–H insertion of rhodium-stabilized acylcarbenesgenerated from diazocarbonyl derivatives, they used an intramolecular Schmidt–Aubé reaction to complete the bicyclic lactam. From a personal standpoint, I find it great that they point out what didn’t work – this is often more useful than a description of what did. Unfortunately, many short articles and letters such as this fail to bother.

Update: Just a few references for those of you who are interested. Tony Kirby has done loads of work in this area, and on related studies, decades prior to this paper.

JOC; 2002; 67, 9288. DOI: 10.1021/jo0206014

JACS; 1998; 120, 7101. DOI: 10.1021/ja980700s

ACIE; 1998; 37, 785. DOI: http://dx.doi.org/10.1002/…

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6 Comments