# The synthesis of non-racemic β-alkyl-β-aryl-disubstituted allyl alcohols and their transformation into allylamines and amino acids bearing a quaternary stereocenter

##### Narczyk, A.; Pieczykolan, Mł.; Stecko, S.

* * *

#### Organic and Biomolecular Chemistry 16(21): 3921-3946

ISSN/ISBN: 1477-0539

* * *

#### 2018

* * *

PMID: 29745946

DOI: 10.1039/c8ob00731d

Document: 004918973

A synthesis of non-racemic β-alkyl-β-aryl allyl alcohols and their transformation into allylamines bearing a quaternary stereogenic center is reported. The allyl alcohols were prepared either by Cu-catalyzed enantioselective reduction of enones or by sequential alkylation/hydrostannylation/Stille coupling of non-racemic propargyl alcohols. The prepared β-alkyl-β-aryl allyl alcohols were converted (after carbamoylation) to the corresponding allylamine derivatives through cyanate-to-isocyanate rearrangement/nucleophilic addition with complete chirality transfer. Varying the nucleophilic agents allowed the preparation of various allylamine derivatives, including carbamates, amides, formamides, ureas, and free amines. The ozonolysis/oxidation of the resulting allylamines provided non-racemic quaternary α-amino acids.

#### Related Documents

[**Chiral azo compounds: enantioselective synthesis and transformations into β-amino alcohols and α-amino acids with a quaternary stereocenter**. Tetrahedron Letters 52(6): 655-657](/content/source/048/561/048561341.php)

* * *

[**The Synthesis of Chiral β,β-Diaryl Allylic Alcohols and Their Use in the Preparation of α-Tertiary Allylamines and Quaternary α-Amino Acids**. Journal of Organic Chemistry 82(11): 5636-5651](/content/source/007/373/007373579.php)

* * *

[**Pd-Catalyzed Allylic Alkylation of gem-Alkyl,Aryl-Disubstituted Allyl Reagents with Ketones: Diastereoselective Construction of Vicinal Tertiary and Quaternary Carbon Centers**. ACS Catalysis 8(4): 3317-3321](/content/source/042/661/042661691.php)

* * *

[**Asymmetric Synthesis of Protected β-Substituted and β,β-Disubstituted β-Amino Acids Bearing Branched Hydroxyalkyl Side Chains and of Protected 1,3-Amino Alcohols with Three Contiguous Stereogenic Centers from Allylic Sulfoximines and Aldehydes**. European Journal of Organic Chemistry 2003(8): 1500-1526](/content/source/044/596/044596857.php)

* * *

[**Transformations of Alkyl 2-(2,2-Disubstituted-ethenyl)amino-3-dimethylaminoprop-2-enoates: Synthesis of Alkyl 3,4-Disubstituted- and Alkyl 1-Acyl-3,4-disubstituted Pyrrole-2-carboxylates**. Synthesis 1999(03): 479-482](/content/source/041/533/041533872.php)

* * *

[**Synthesis of Enantiopure Isosteres of Amino Acids Containing a Quaternary Stereocenter: Experimental and Computational Evaluation of a Novel Class of Atropisomers**. European Journal of Organic Chemistry 2018(46): 6524-6536](/content/source/044/605/044605875.php)

* * *

[**3,3-Disubstituted allyl alcohols from palladium-catalyzed coupling of hydroaluminated propargyl alcohols with aryl iodides**. Journal of Organic Chemistry 67(7): 2125-2130](/content/source/007/352/007352171.php)

* * *

[**Cu(i)-catalyzed Michael addition of ketiminoesters to β-trifluoromethyl β,β-disubstituted enones: rapid access to 1-pyrrolines bearing a quaternary all-carbon stereocenter**. Organic Chemistry Frontiers 4(9): 1772-1776](/content/source/040/448/040448153.php)

* * *

[**I2/Fe(NO3)3·9H2O-catalyzed oxidative synthesis of aryl carboxylic acids from aryl alkyl ketones and secondary benzylic alcohols**. Tetrahedron Letters 59(49): 4349-4354](/content/source/048/569/048569927.php)

* * *

[**Catalytic Asymmetric Synthesis of Functionalized α,α-Disubstituted α-Amino Acid Derivatives from Racemic Unprotected α-Amino Acids via in-situ Generated Azlactones**. Advanced Synthesis and Catalysis 354(8): 1443-1449](/content/source/052/840/052840167.php)