Jacobsen and colleagues (JACS, 2013, 135 (18), 6747) presented a very nice communication describing the organocatalysed generation of N-hydroxypyrrolidines with modest to high enantioselectivity.

H Mayr et al, (JACS, 2013, 135 (17), 6579) reports on the electrophilicities of benzaldehyde-derived iminium ions, producing a scale as shown below which I thought may be of use to chemists in the battle toward achieving the balance between a nucleophile and electrophile.  Good luck!

Since the Mitsunobu reaction was first introduced in 1967, it has proved an invaluable reaction in discovery chemistry yet process chemists have been reluctant to use it on large scale because of the toxicity of DEAD, thermal hazards and the difficulties with waste streams.

 The reaction can be extended to produce chiral pyrrolidones if chiral iridium catalysts are first used to make the allylic formamide, followed by Ru catalysed cyclisation ( J Amer Chem Soc, 2013, 135, 6814).

I was intrigued to see a paper describing the formation of enantiomerically pure α-functionalised Grignard reagents (P O’Brien et al, JACS, 2013, 135 (21), 8071).  Perhaps I had missed earlier reports, but was especially interested in the generation of the configurationally stable ‘anionic’ centre.

A few years ago chemists at Boehringer Ingelheim reported the reductive acetylation of oximes¹ to produce N-acetylenamides which are good substrates for asymmetric hydrogenation.

A few years ago chemists at Boehringer Ingelheim reported the reductive acetylation of oximes¹ to produce N-acetylenamides which are good substrates for asymmetric hydrogenation.