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Articles Archive for January 2007

Still In The RBF »

[31 Jan 2007 | 18 Comments | 78,405 views]

Snapper, Williams and Deak. JACS, 2007, 129, 486. DOI: 10.1021/ja0674340.

An extraordinary synthesis of this simple-looking guaiane natural product (along with it’s exo-methylene analogue, pleocarpenene), Marc Snapper has once again used deft control of pericyclic reactions to produce some extremely odd looking intermediates in this synthesis. As regular readers will know, I tend to use a disconnection-based retrosynthesis to explain the synthetic plan, but as you can see, Snapper’s approach makes this a little tricky!

From this retro, it’s clear that the double ring-expansion (is that the correct term?) is key to …

Still In The RBF »

[29 Jan 2007 | 3 Comments | 8,057 views]

Danishefsky, Li, Chan and Heimann. ACIEE, 2006, EarlyView. DOI: 10.1002/anie.200604072.
In a pair of papers in Angewandte, Danishefsky has completed some rather interesting work on the mechanisms of formation and the total synthesis of the structurally interesting alkaloid, Phalarine. This little nugget was isolated from blue canary grass, but there’s precious little data on it’s biological profile, so lets just look at making it for the chemistry’s sake!

After a little mundane heterocycle synthesis, things heat up, literally… after cleaving the MOM group, cyclisation / rearrangement leaves them with the core of …

Still In The RBF »

[26 Jan 2007 | 14 Comments | 4,591 views]

Jung and Murakami. JACS, 2007, 9, 461. DOI: 10.1021/ol062811z.

Just a quickie for the weekend; a nice Org Lett by Jung, published at the start of the year. The target has an interesting biological profile, with anti-inflammatory activity and inhibition of nitric oxide production. The potency of the latter is also impressive interesting (see comments), with an IC50 of 28μM. The isolation was published back in 2002, so I’m slightly surprised that this is the first synthesis of such an attractive target, but this is a great approach to a congested …

Still In The RBF »

[22 Jan 2007 | 14 Comments | 6,068 views]

Morimoto, Okita, Takaishi and Tanaka. ACIEE, 2006, EarlyView. DOI: 10.1002/anie.200603806.
Somewhat similar in structure to silvaticin, blogged here back in October, intricatetraol is an interesting C2 symmetric bis-THF. This feature lead to a somewhat unsurprising disconnection along the axis of symmetry, to reveal a dimerisation metathesis and reduction strategy. As dull as that might be, the rest of the synthesis was a whole lot more exciting, if based predominately on epoxidation/opening. However, it’s quite the master-class, so lets look at the epoxidation strategy at a whole. As you can see, the …

Editorial »

[18 Jan 2007 | 14 Comments | 4,153 views]

Yup, the title says it all. I had planned to do this for a while, but I was forgot in the hiatus of The Move. However, a more thorough investigation of the brilliant ChemBark led me to a reminder! I’m leaving it up to you lovely readers to suggest your favourites, then I’ll add a poll of ten (in a week). Once a synthesis has been suggested, it’s been suggested, so there’s no need to post it twice, and please add a DOI if I didn’t blog it (shame on …

Still In The RBF »

[17 Jan 2007 | 6 Comments | 4,893 views]

Williams, Robinson, Nevill, and Reddy. ACIEE, 2006, EarlyView. DOI: 10.1002/anie.200603853.
Another appearance for the Nazarov rearrangement in this smart synthesis of Fusicoauritone, an interesting terpene with a dicyclopenta[a,d]cyclooctane ring system. Of course, many related structures have been made before, but this appears to be the first synthesis of this molecule. Williams et al. have used a partially-biomimetic approach to the ring system, first creating an eleven-member ring, then closing to form a 5,8-system. However, the cyclisation precursor is hardly non-trivial, so lets look at that first:
The synthesis of that beast begins …

Still In The RBF »

[13 Jan 2007 | 9 Comments | 6,493 views]

Frontier, He, Huang and Sun. JACS, 2006, ASAP. DOI: 10.1021/ja068150i.

Well, I’m back. Not quite up to speed – there’s been loads of totally synthetic action over the last three weeks, but I’m working my way through the journals, and posting as I go. As an aside, I’d like to thank everyone at Oxford for their welcome, kindness and support – moving labs isn’t easy or fun, but they’ve been great (especially the Fleet group :))
On with the synthesis! I’m starting with a great JACS article, posted at the close of …