(−)-(2S,3R,Z)‑Nakinadine A: First Asymmetric Synthesis and Absolute Configuration Assignment

Mannich-type reaction of methyl phenylacetate with the N-tert-butylsulfinyl imine derived from (R)-tert-butylsulfinamide and (Z)-14-(pyridin-3′-yl)­tetradec-11-enal has been used as the key step in the first asymmetric synthesis of (−)-nakinadine A. Both the 2,3-syn- and 2,3-anti-diastereoisomers were prepared; comparison of spectroscopic and specific rotation data facilitated assignment of the absolute (2S,3R,Z)-configuration within the natural product. (−)-(2S,3R,Z)-Nakinadine A was prepared in 10 steps from 11-bromo­undecan-1-ol, in 10% overall yield, 97:3 dr [(Z):(E) ratio], and >98% ee.