Synlett 2017; 28(05): 615-619
DOI: 10.1055/s-0036-1588382
letter
© Georg Thieme Verlag Stuttgart · New York

Synthesis of N,N′-Dialkylated Cyclohexane-1,2-diamines and Their Application as Asymmetric Ligands and Organocatalysts for the Synthesis of Alcohols

Alexey A. Tsygankov
a  Moscow Chemical Lyceum, Tamozhenniy proezd 4, Moscow, Russian Federation
,
Man-Seog Chun
b  Korea Science Academy of KAIST, 105-47, Baegyanggwanmun-ro, Busanjin-gu, 47162 Busan, Republic of Korea
,
Alexandra D. Samoylova
a  Moscow Chemical Lyceum, Tamozhenniy proezd 4, Moscow, Russian Federation
,
Seongyeon Kwon
b  Korea Science Academy of KAIST, 105-47, Baegyanggwanmun-ro, Busanjin-gu, 47162 Busan, Republic of Korea
,
Yuliya M. Kreschenova
a  Moscow Chemical Lyceum, Tamozhenniy proezd 4, Moscow, Russian Federation
,
Suhyeon Kim
b  Korea Science Academy of KAIST, 105-47, Baegyanggwanmun-ro, Busanjin-gu, 47162 Busan, Republic of Korea
,
Euijin Shin
b  Korea Science Academy of KAIST, 105-47, Baegyanggwanmun-ro, Busanjin-gu, 47162 Busan, Republic of Korea
,
Jinho Oh
b  Korea Science Academy of KAIST, 105-47, Baegyanggwanmun-ro, Busanjin-gu, 47162 Busan, Republic of Korea
,
Tatyana V. Strelkova
c  A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova str. 28, 119991 Moscow, Russian Federation   Email: Chusov@ineos.ac.ru
,
Valerii S. Kolesov
c  A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova str. 28, 119991 Moscow, Russian Federation   Email: Chusov@ineos.ac.ru
,
Fedor I. Zubkov
d  Peoples Friendship University of Russia, Dept Organic Chemistry, 6 Miklukho-Maklaya St, Moscow 117198, Russian Federation
,
Sergei E. Semenov
a  Moscow Chemical Lyceum, Tamozhenniy proezd 4, Moscow, Russian Federation
,
Ivan V. Fedyanin
c  A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova str. 28, 119991 Moscow, Russian Federation   Email: Chusov@ineos.ac.ru
,
Denis Chusov*
a  Moscow Chemical Lyceum, Tamozhenniy proezd 4, Moscow, Russian Federation
c  A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova str. 28, 119991 Moscow, Russian Federation   Email: Chusov@ineos.ac.ru
d  Peoples Friendship University of Russia, Dept Organic Chemistry, 6 Miklukho-Maklaya St, Moscow 117198, Russian Federation
› Author Affiliations
Further Information

Publication History

Received: 05 October 2016

Accepted after revision: 29 November 2016

Publication Date:
15 December 2016 (online)

Abstract

A series of N,N′-dialkylated derivatives of (1R,2R)-cyclohexane-1,2-diamine were synthesized, and a new approach to the one-pot preparation of this type of amine was demonstrated. The prepared diamines were used as organocatalysts for the two-step synthesis of α-hydroxy γ-keto esters from arenes, chlorooxoacetates, and ketones; they were also used as chiral ligands for Meervein–Ponndorf–Verley reductions and Henry reactions.

Supporting Information

 
  • References and Notes

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  • 12 Diamines 3ak; General Procedure from Schiff Bases 2ak NaBH4 (2.1 equiv) was added portionwise over 40 min to a solution of the appropriate Schiff base 2 (1.0 equiv) in MeOH (4 mL/mmol of Schiff base) at r.t. The mixture was refluxed with stirring for 1 h then cooled to r.t. H2O (5 mL/mmol of Schiff base) was added, the mixture was extracted with CH2Cl2 (3 × 4 mL/mmol of Schiff base), and the organic layer was concentrated. If any aldehyde remained in the mixture, the residue was dissolved in 35% aq HCl (1 mL/mmol of Schiff base) and the solution was washed with CH2Cl2 (3 × 4 mL/mmol of Schiff base). Excess K2CO3 (4.5 equiv) was added to the aqueous phase, which was extracted with CH2Cl2 (3 × 3 mL/mmol of Schiff base). The organic layers were combined, dried, and concentrated to give an oily product. If the product was not sufficiently pure, it was purified by column chromatography. (1R,2R)-N,N′-Bis(4-chlorobenzyl)cyclohexane-1,2-diamine (3e) Yellow oil; yield: 2.45 g (48%); [α]D 25 –64.7 (с 1.2, CHCl3). 1H NMR (600 MHz, CDCl3): δ = 7.29 (d, J = 8.4 Hz, 4 H), 7.25 (d, J = 8.4 Hz, 4 H), 3.88 (d, J = 13.4 Hz, 2 H), 3.64 (d, J = 13.4 Hz, 2 H), 2.28–2.24 (m, 2 H), 2.17–2.12 (m, 2 H), 1.76–1.71 (m, 2 H), 1.27–1.18 (m, 2 H), 1.11–0.97 (m, 2 H). 13C NMR (101 MHz, CDCl3): δ = 139.6, 132.5, 129.5, 128.6, 61.2, 50.5, 32.0, 25.5; MS (ESI): m/z = 363, 365, 367 [M + H]+.
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