Synthesis of 1,3-Diaminated Stereotriads via Rearrangement of 1,4-Diazaspiro[2.2]pentanes

• Published in: Organic letters Vol. 14; no. 7; pp. 1704 - 1707
• Main Authors: Weatherly, Cale D, Rigoli, Jared W, Schomaker, Jennifer M
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 06.04.2012; Amer Chemical Soc
• Subjects: Alkadienes - chemistry; Aza Compounds - chemical synthesis; Aza Compounds - chemistry; Catalysis; Chemistry; Chemistry, Organic; Imidazolidines - chemical synthesis; Imidazolidines - chemistry; Ketones - chemical synthesis; Ketones - chemistry; Molecular Structure; Physical Sciences; Pyrimidines - chemical synthesis; Pyrimidines - chemistry; Pyrroles - chemical synthesis; Pyrroles - chemistry; Science & Technology; Spiro Compounds - chemistry; PLATFORM; MANNICH REACTION; AMINATION; ASYMMETRIC-SYNTHESIS; STRATEGY; IMINES; RING; ALDEHYDES; DERIVATIVES
• ISSN: 1523-7060; 1523-7052
• DOI: 10.1021/ol300269u

The synthesis of 1,3-diaminated stereotriads via the bis-aziridination of allenes is reported. The reactive 1,4-diazaspiro[2.2]pentane intermediates undergo a mild Brønsted acid-promoted rearrangement to yield 1,3-diaminated ketones in good yields with excellent stereocontrol. Directed reduction of the ketone can be achieved to yield a C–N/C–O/C–N stereotriad in high dr. The ability to transfer the axial chirality of the substrates to the products allows for the facile preparation of enantioenriched stereotriads from allenes in two simple steps.