1996
DOI: 10.1021/jo960047w
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Synthesis of Enantiopure Primary Amines by Stereoselective Ring Opening of Chiral Octahydro-1,3-benzoxazines by Grignard and Organoaluminum Reagents

Abstract: Chiral 1,3-perhydrobenzoxazines 1, 2, and 9-14, prepared by condensation of 8-(benzylamino)menthol with different aldehydes, react with alkylmagnesium bromides and trimethylaluminum leading to the open amino alcohols 3a-d, 4a-d, and 15-20 in excellent chemical yields and good to excellent diastereomeric excess. The sequential elimination of the menthol appendage by heating with P(2)O(5) and the benzyl group by hydrogenolysis lead to primary amines 7a-d, 8a-d, and 27-30 in excellent chemical yields and ee. The … Show more

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Cited by 52 publications
(31 citation statements)
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“…17 In summary, we have shown that positional isomers of 2,3-disubstituted perhydro-1,3-benzoxazines, bearing an aryl group and a double bond as substituents, react in a different way under similar intramolecular Heck conditions. Cyclization compounds resulting from 2-vinyl-3-aryl substituted substrates suffer additional readdition of palladium hydride species, and syn-dealkoxypalladation with concomitant ring opening-ring closing to the rearranged enamines 9.…”
Section: Scheme 2 Heck Cyclization Of Compounds 1a-ementioning
confidence: 86%
“…17 In summary, we have shown that positional isomers of 2,3-disubstituted perhydro-1,3-benzoxazines, bearing an aryl group and a double bond as substituents, react in a different way under similar intramolecular Heck conditions. Cyclization compounds resulting from 2-vinyl-3-aryl substituted substrates suffer additional readdition of palladium hydride species, and syn-dealkoxypalladation with concomitant ring opening-ring closing to the rearranged enamines 9.…”
Section: Scheme 2 Heck Cyclization Of Compounds 1a-ementioning
confidence: 86%
“…1,3-Oxathianes were used as chiral sulfides in asymmetric syntheses of mono-and diaryloxiranes [189,190] and trans-cyclopropanes [191,192] and were subjected to phosphorylation to obtain phospholipid analogs [193]. 1,3-Oxazines were reported as stereoinductors in the synthesis of optically pure compounds [194][195][196][197][198], and 6-arylbenzoxazines are potent nonsteroidal progesterone receptor agonists [199].…”
Section: Scheme 59mentioning
confidence: 99%
“…A large number of natural products such as α‐ and β‐pinene, 2‐ and 3‐carene, and (+)‐pulegole serve as important starting materials for the synthesis of bi‐ and trifunctional chiral compounds and heterocycles. Monoterpene‐based 1,2‐ and 1,3‐amino alcohols have been demonstrated to be excellent chiral auxiliaries in a wide range of stereoselective transformations, including intramolecular radical cyclizations, intramolecular [2+2] photocycloaddition, and Grignard addition …”
Section: Introductionmentioning
confidence: 99%
“…Monoterpene-based 1,2-and 1,3-amino alcohols have been demonstrated to be excellent chiral auxiliaries in aw ide range of stereoselective transformations, including intramolecular radical cyclizations, [11] intramolecular [2+ +2] photocycloaddition, [12] and Grignard addition. [13,14] Furthermore,a minodiols, combining the chemical properties of 1,2-and 1,3-amino alcohols derived fromn aturally occurring terpenes, are excellent startingm aterials and catalysts of stereoselectives ynthesis. [15][16][17][18][19][20] Moreover,a minodiols are excellent buildingb locks for the synthesis of 1,3-oxazinesa nd oxazolidines.…”
Section: Introductionmentioning
confidence: 99%