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Diastereoselective Regiodivergent Mannich Versus Tandem Mannich‐Cyclization Reactions
Author(s) -
Zhang Wenzhong,
Wang Xin,
Zhu Biqing,
Zhu Di,
Han Jianlin,
Wzorek Alicja,
Sato Azusa,
Soloshonok Vadim A.,
Zhou Jie,
Pan Yi
Publication year - 2017
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201701066
Subject(s) - chemistry , trifluoromethyl , tandem , mannich reaction , reactivity (psychology) , thiocyanate , organic chemistry , combinatorial chemistry , primary (astronomy) , adduct , catalysis , medicine , alkyl , materials science , alternative medicine , pathology , composite material , physics , astronomy
In the present work, we report the addition reactions between ( S )‐ and ( R )‐ N ‐ t ‐butylsulfinyl‐3,3,3‐trifluoro‐acetaldimine and tertiary enolates derived from α‐thiocyanate ketones. We demonstrate that these reactions feature unusual regiodivergence, affording either the direct Mannich adducts (NaOAc/THF) or the products of tandem Mannich addition‐cyclization (Na 2 CO 3 /DMF) reactions. The latter represents a new class of spirocyclic trifluoromethyl‐containing aziridines unavailable by other approaches. The reactions show wide structural generality, rendering them of certain synthetic value for preparation of new fluorine‐containing polyfunctional compounds of biological relevance. Mechanistic rationale for the observed reactivity and stereochemical outcome is provided.