A highly diastereoselective total synthesis of (+)-pseudohygroline (1) starting from D-proline is described using Wittig olefination and MacMillan-α-hydroxylation as key reactions. (+)-Pseudohygroline is an important molecule in alkaloid chemistry as it was prepared as part of the first chemical proof of the absolute stereochemistry of biosynthetically important (+)-hygroline (2) and (+)-hygrine (3).
HartmannT. (1999) Chemical ecology of pyrrolizidine alkaloids. Planta, 207, 483–495
2.
SchulzS. (1998) Insect-plant interactions-metabolism of plant compounds to pheromones and allomones by lepidoptera and leaf beetles. European Journal of Organic Chemistry, 1, 13–20.
LukesR, KovJ, KloubekJ, Bl-lhaK. (1960) Absolute configuration of hygrine. Collection of Czechoslovak Chemical Communications, 25, 483–491.
8.
ShonoT, MatsumuraY, TsubataK, UchidaK. (1986) Synthesis of optically active piperidine and pyrrolidine alkaloids from L-lysine, L-ornithine, or L-proline using anodic oxidation as key steps. Journal of Organic Chemistry, 51, 2590–2592
9.
KnightDW, SalterR. (1999) Activation of the reverse-cope elimination by allylic oxygen functions: Syntheses of (-)-hygroline and (+)-pseudohygroline. Tetrahedron Letters, 40, 5915–5918
10.
TakahataH, KubotaM, MomoseT. (1997) New synthesis of all the four isomers of 2-(2-hydroxypropyl)pyrrolidines via iterative asymmetric dihydroxylation to cause enantiomeric enhancement. Tetrahedron Asymmetry, 8, 2801–2810
11.
EniergaG, HocklessDCR, PerlmutterP, RoseM, SjobergS, WongK. (1998) An enantioselective synthesis of (+)-pseudohygroline. Tetrahedron Letters, 39, 2813–2814
12.
EniergaG, EspirituM, PerlmutterP, PhamN, RoseM, SjobergS, ThienthongN, WongK. (2001) Intramolecular amidomercurations under allylic control: a stereoselective synthesis of (+)-pseudohygroline and (+)-3-hydroxypyrrolizidine. Tetrahedron Asymmetry, 12, 597–604
13.
YadavJS, NarasimhuluG, ReddyNM, ReddyBVS. (2010) Total synthesis of (+)-pseudohygroline. Tetrahedron Letters, 51, 1574–1577
14.
LinigerM, EstermannK, AltmannKH. (2013) Total synthesis of hygrolines and pseudohygrolines. Journal of Organic Chemistry, 78, 11066–11070
15.
ColdhamI, LeonoriD. (2010) Regioselective and stereoselective copper(I)-promoted allylation and conjugate addition of N-boc-2-lithiopyrrolidine and N-boc-2-lithiopiperidine. Journal of Organic Chemistry, 75, 4069–4077
16.
DaviesSG, FletcherAM, RobertsPM, SmithAD. (2009) Asymmetric synthesis of Sedum alkaloids via lithium amide conjugate addition. Tetrahedron, 65, 10192–10213
17.
ChinmayB, SantoshGT. (2011) Synthesis of (-)-hygrine, (-)-norhygrine, (-)-pseudohygroline and (-)-hygroline via Nef reaction. Tetrahedron Letters, 52, 6566–6568.
18.
GreenTW, WutsPGM. (1999) Protective groups in organic synthesis. Wiley Interscience, New York, 518–525 & 736-739
19.
HarrisonTJ, GregoryRD. (2005) An expeditious, high-yielding construction of the food aroma compounds 6-acetyl-l,2,3,4-tetrahydropyridine and 2-acetyl-l-pyrroline. Journal of Organic Chemistry, 70, 10872–10874.
20.
CoreyEJ, MarafatA, LaguzzaBC. (1981) Total synthesis of 5S, 12S-dihydroxy-6,10-E,8,14-Z-eicosatetraenoic acid (5S,12S-di-HETE) (2), a new human metabolite of arachidonic acid. Tetrahedron Letters, 22, 3339–3342.
WangPS, LiangCK, LeungMK. (2005) An improved Ullmann-Ukita-Buchwald-Li conditions for Cul-catalyzed coupling reaction of 2-pyridones with aryl halides. Tetrahedron, 61, 2931–2939
23.
NarayanaMS, NageswarYVD. (2011) o-Iodoxybenzoic acid (IBX): a versatile reagent for the synthesis of N-substituted pyrroles mediated by β-cyclodextrin in water. Tetrahedron Letters, 52, 4481–4484.
24.
SatohT, NanbaK, SuzukiS. (1971) Direct proline catalyzed asymmetric α-aminooxylation of aldehydes. Chemical & Pharmaceutical Bulletin, 19, 817–820
25.
YadavJS, RameshK, ReddyUVS, ReddyBVS, GhamdiAK. (2011) The stereoselective total synthesis of (+)-18-(6S,9R,10R)-bovidic acid. Tetrahedron Letters, 52, 2943–2945.
26.
MangionIK, MacMillanDWC, (2005) Total synthesis of brasoside and littoralisone. Journal of the American Chemical Society, 127, 3696–3697
27.
VarseevGN, MaierME. (2007) Enantioselective total synthesis of (+)-neosymbioimine. Organic Letters, 9, 1461–1464
28.
BrownSP, BrochuM, SinzCJ, MacMillianDWC. (2003) Total synthesis of brasoside and littoralisone. Journal of the American Chemical Society, 125, 10808–10809
29.
ZhongG. (2003) A facile and rapid route to highly enantiopure 1,2-diols by novel catalytic asymmetric α-aminoxylation of aldehydes. Angewandte Chemie International Edition, 42, 4247–4250
30.
HayashiY, YamaguchiJ, HibinoK, ShojiM. (2003) Direct proline catalyzed asymmetric α-aminooxylation of aldehydes. Tetrahedron Letters, 44, 8293–8296.
31.
KongX, GrindleyTB. (1994) Control of regioselectivity in reactions of dialkylstannylene acetals. Part I. A dramatic reversal of regioselectivity in mono-p-toluenesulfonation reactions. Canadian Journal of Chemistry, 72, 2396–2404.
32.
DengW, OvermanLE. (1994) Enantioselective total synthesis of either enantiomer of the antifungal antibiotic preussin (L-657,398) from (S)-phenylalanine. Journal of the American Chemical Society, 116, 11241–11250.
