Short Total Synthesis of (-)-Lupinine and (-)-Epiquinamide by Double Mitsunobu Reaction

被引：14

作者：

Silva Santos, Leonardo ^{[1
]}

Mirabal-Gallardo, Yaneris ^{[1
]}

Shankaraiah, Nagula ^{[1
,2
]}

Simirgiotis, Mario J. ^{[3
]}

机构：

[1] Univ Talca, Chem Inst Nat Resources, Lab Asymmetr Synth, Talca, Chile

[2] NIPER, Hyderabad 500037, Andhra Pradesh, India

[3] Univ Antofagasta, Fac Basic Sci, Dept Chem, Lab Nat Prod, Antofagasta, Chile

来源：

SYNTHESIS-STUTTGART | 2011年 / 01期

关键词：

quinolizidine alkaloids; azido reduction; nickel boride; microwave irradiation; Mitsunobu reaction; ENANTIOSELECTIVE TOTAL-SYNTHESIS; N-ACYLIMINIUM IONS; NICKEL BORIDE; AZABICYCLIC ALCOHOLS; CONSTRUCTION; EPIQUINAMIDE; ALKALOIDS; (+)-EPIQUINAMIDE; DERIVATIVES; LUPININE;

D O I：

10.1055/s-0030-1258356

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Alternative total syntheses of (-)-lupinine (1) and (-)-epiquinamide (2) have been described via the key intermediate 3 obtained from the addition of 2-trialkylsilyloxyfuran 5 to N-acyliminium intermediate derived from 4. The major R, R-isomer 8 obtained from the Mannich reaction was converted into its R, S-isomer through Mitsunobu reaction. Then, a second Mitsunobu reaction of 3 led to cyano 9 and azido 11 derivatives, which were converted into 1 and 2 in 33 and 36% overall yield from 4, respectively. The synthetic route is amenable for the generation of several quinolizidine alkaloids.

引用

页码：51 / 56

页数：6

共 38 条

[1] AZABICYCLIC ALCOHOLS .1. STEREOCHEMISTRY OF HYDROXYQUINOLIZIDINES
AARON, HS
RADER, CP
WICKS, GE
[J]. JOURNAL OF ORGANIC CHEMISTRY, 1964, 29 (08) : 2248 - &
[2] Short Access to (+)-Lupinine and (+)-Epiquinamide via Double Hydroformylation
Airiau, Etienne
Spangenberg, Thomas
Girard, Nicolas
Breit, Bernhard
Mann, Andre
[J]. ORGANIC LETTERS, 2010, 12 (03) : 528 - 531
[3] CATALYTIC HYDROGENATION .5. REACTION OF SODIUM BOROHYDRIDE WITH AQUEOUS NICKEL SALTS - P-1 NICKEL BORIDE, A CONVENIENT, HIGHLY ACTIVE NICKEL HYDROGENATION CATALYST
BROWN, CA
[J]. JOURNAL OF ORGANIC CHEMISTRY, 1970, 35 (06) : 1900 - +
[4] FURAN-BASED, PYRROLE-BASED, AND THIOPHENE-BASED SILOXYDIENES FOR SYNTHESES OF DENSELY FUNCTIONALIZED HOMOCHIRAL COMPOUNDS
CASIRAGHI, G
RASSU, G
[J]. SYNTHESIS-STUTTGART, 1995, (06): : 607 - 626
[5] Evolution of a strategy for the synthesis of structurally complex batzelladine alkaloids. Enantioselective total synthesis of the proposed structure of batzelladine F and structural revision
Cohen, F
Overman, LE
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (08) : 2594 - 2603
[6] QUINOLIZINES .4. THE SYNTHESIS OF 1-AMINOQUINOLIZINIUM SALTS
COLLICUTT, AR
JONES, G
[J]. JOURNAL OF THE CHEMICAL SOCIETY, 1960, (OCT): : 4101 - 4105
[7] The addition of 2-tert-butyldimethylsilyloxyfuran to cyclic N-acyliminium ions containing cyclohexyl-based chiral auxiliaries
D'Oca, MGM
Pilli, RA
Vencato, I
[J]. TETRAHEDRON LETTERS, 2000, 41 (50) : 9709 - 9712
[8] Diastereoselection of the addition of silyloxyfurans to five-, six- and seven-membered N-acyliminium ions
de Oliveira, MDF
Santos, LS
Pilli, RA
[J]. TETRAHEDRON LETTERS, 2001, 42 (40) : 6995 - 6997
[9] Epiquinamide: A Poison That Wasn't from a Frog That Was
Fitch, Richard W.
Sturgeon, Gordon D.
Patel, Shaun R.
Spande, Thomas F.
Garraffo, H. Martin
Daly, John W.
Blaauw, Richard H.
[J]. JOURNAL OF NATURAL PRODUCTS, 2009, 72 (02): : 243 - 247
[10] Bioassay-guided isolation of epiquinamide, a novel quinolizidine alkaloid and nicotinic agonist from an Ecuadoran poison frog, Epipedobates tricolor
Fitch, RW
Garraffo, HM
Spande, TF
Yeh, HJC
Daly, JW
[J]. JOURNAL OF NATURAL PRODUCTS, 2003, 66 (10): : 1345 - 1350

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