The First Asymmetric Synthesis of 1,4-Dideoxy-1,4-imino-d-talitol

Abstract

The first stereoselective synthesis of 1,4-dideoxy-1,4-imino-d-Talitol has been achieved in 24% overall yield from conveniently protected (S)-glyceraldimine (1), which is easily prepared from inexpensive d-mannitol. The synthesis is based on the addition of vinylmagnesium bromide to this N-benzylimine followed by N-acylation, ring-closing metathesis and asymmetric dihydroxylation. In this synthesis as many as three stereogenic centres are constructed with total stereoselectivity.

Key words

stereoselective synthesis - alkaloids - addition reactions - metathesis - dihydroxylations

References

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8

Spectral data for compound 6: ¹H NMR (400 MHz, CDCl₃): δ = 3.24 [dd, 1 H, J = 10.7 Hz, J = 3.2 Hz, CH ₂ (OC)CH- (OC)CHN], 3.29 [dd, 1 H, J = 10.7 Hz, J = 5.6 Hz, CH ₂ (OC)CH(OC)CHN], 3.81 [ddd, 1 H, J = 5.6 Hz, J = 5.6 Hz, J = 3.2 Hz, CH₂(OC)CH(OC)CHN], 4.04 (d, 1 H, J = 15.2, NCH ₂ Ph), 4.07 [ddd, 1 H, J = 5.6 Hz, J = 3.2 Hz, J = 1.6 Hz, CH₂(OC)CH(OC)CHN], 4.32 (s, 2 H, OCH ₂ Ph), 4.42 (d, 1 H, J = 11.6 Hz, OCH ₂ Ph), 4.59 (d, 1 H, J = 11.6 Hz, OCH ₂ Ph), 4.95 (d, 1 H, J = 15.2 Hz, NCH ₂ Ph), 6.12 (dd, 1 H, J = 6.0 Hz, J = 1.6 Hz, NCHCH=CHCO), 6.99-7.02 (m, 3 H, NCHCH=CHCO, CH _arom), 7.15-7.29 (m, 15 H, CH _arom). ¹³C NMR (100 MHz, CDCl₃): δ = 44.5, 63.1, 69.2, 72.4, 73.3, 76.8, 127.4, 127.5, 127.7, 127.8, 128.3, 128.6, 137.1, 137.5, 137.6, 145.5, 145.6, 171.6