NOESY experiment of diastereomer 10α (3S, 5R) …….(3S,5R)-3-Benzyl-5-isobutyl-1,3,4,5-tetrahydro-2H-thieno[3,2-e]- [1,4]diazepin-2-one (10α)

NOESY experiment of diastereomer 10α (3S, 5R)

(3S,5R)-3-Benzyl-5-isobutyl-1,3,4,5-tetrahydro-2H-thieno[3,2-e]- [1,4]diazepin-2-one (10α):

Pale yellow solid, 50% (64.0 mg),

m.p. 66.7–67.4 °C.

[α]D 29 = –122.2 (c = 1.0, MeOH).

1 H NMR (CDCl3, 300 MHz): δ = 0.90 (d, J = 6.3 Hz, 3 H), 0.92 (d, J = 6.6 Hz, 3 H), 1.36–1.54 (m, 2 H), 1.81 (m, 1 H), 2.08 (s, 1 H), 3.13 (d, J = 5.1 Hz, 2 H), 3.93 (t, J = 5.1 Hz, 1 H), 4.67 (dd, J = 3.0, J = 9.9 Hz, 1 H), 7.15–7.30 (m, 8 H) ppm.

13C NMR (CDCl3, 75 MHz): δ = 21.48, 23.79, 24.71, 36.81, 42.09, 59.63, 73.76, 111.68, 120.97, 125.09, 126.92, 126.97, 128.70, 129.83 (2 C), 135.11, 136.90, 172.65 ppm.

LC–MS (ESI+): m/z = 315.2 [M + H]+.

HRMS: calcd. for C18H23N2OS 315.1531 [M + H]+; found 315.1531

10.1002/ejoc.201500943

///////////

trans-2-(benzo[d][1,3]dioxol-5-yl)-2-methylcyclopropane-1-carbonitrile

trans-2-(benzo[d][1,3]dioxol-5-yl)-2-methylcyclopropane-1-carbonitrile

yellowish solid (53 mg, 66%);

m.p. = 72 °C;

1 H-NMR (600 MHz, CDCl3): δ = 6.77 – 6.71 (m, 3H), 5.94 (s, 2H), 1.63 – 1.59 (m, 4H), 1.50 (dd, J = 9.1, 5.0 Hz, 1H), 1.26 (t, J = 5.3 Hz, 1H);

13CNMR (151 MHz, CDCl3): δ = 147.80, 146.73, 136.69, 120.64, 120.23, 108.28, 108.17, 101.19, 28.75, 23.86, 21.40, 11.30;

HRMS (ESI): m/z calc. for [C12H11O2NK]: 240.0414, found 240.04204;

IR (KBr): νmax/cm-1 = 2972, 2897, 2231, 1490, 1457, 1434, 1349, 1226, 1080, 1033, 924, 869, 808, 728.

1H NMR PREDICT

13C NMR PREDICT

 Green Chem., 2017, Advance Article

DOI: 10.1039/C7GC00602K, Communication

//////////


C[C@@]1([C@H](C#N)C1)C2=CC(OCO3)=C3C=C2

2-{[6-Chloro-3-methyl-2,4-dioxo-3,4-dihydropyrimidin-1(2H)-yl]methyl}-4-fluorobenzonitrile

2-{[6-Chloro-3-methyl-2,4-dioxo-3,4-dihydropyrimidin-1(2H)-yl]methyl}-4-fluorobenzonitrile (4)

white solid . Mp: 193–195 °C.
1H NMR (400 MHz, CDCl3) δ (ppm): 7.74–7.76(m, 1H), 7.14–7.17 (m, 1H), 6.95–6.97 (m, 1H), 6.05 (s, 1H), 5.51 (s, 2H), 3.40 (s, 3H).

Efficient synthesis of isoquinolines in water by a Pd-catalyzed tandem reaction of functionalized alkylnitriles with arylboronic acids

Efficient synthesis of isoquinolines in water by a Pd-catalyzed tandem reaction of functionalized alkylnitriles with arylboronic acids

Green Chem., 2017, Advance Article
DOI: 10.1039/C7GC00267J, Paper
Kun Hu, Linjun Qi, Shuling Yu, Tianxing Cheng, Xiaodong Wang, Zhaojun Li, Yuanzhi Xia, Jiuxi Chen, Huayue Wu
Pd-catalyzed tandem reaction of functionalized alkylnitriles with arylboronic acids for the synthesis of diverse isoquinolines in water.

Efficient synthesis of isoquinolines in water by a Pd-catalyzed tandem reaction of functionalized alkylnitriles with arylboronic acids

Kun Hu,a   Linjun Qi,a   Shuling Yu,a   Tianxing Cheng,a  Xiaodong Wang,a   Zhaojun Li,b   Yuanzhi Xia,a  Jiuxi Chen*a and   Huayue Wua  
*Corresponding authors
aCollege of Chemistry & Materials Engineering, Wenzhou University, Wenzhou 325035, China
E-mail: jiuxichen@wzu.edu.cn
bInstitute of Agricultural Resources and Regional Planning, Chinese Academy of Agricultural Sciences, Key Laboratory of Plant Nutrition and Fertilizer, Ministry of Agriculture, Beijing, China
Green Chem., 2017, Advance Article

DOI: 10.1039/C7GC00267J, 

A palladium-catalyzed tandem reaction of 2-(cyanomethyl)benzonitriles or 2-(2-carbonylphenyl)acetonitriles with arylboronic acids in water has been developed for the first time. This reaction features good functional group tolerance and provides a new strategy for the synthesis of diverse isoquinolines under mild conditions. The use of water as the reaction medium makes the synthesis process environmentally benign. Preliminary mechanistic experiments indicate that the major reaction pathway involves carbopalladation of the C(sp3)–cyano group and subsequent intramolecular cyclization findings that were further supported by density functional theory (DFT) calculations.
Capture
STR1

1,3-Diphenylisoquinoline (3a). Pale-yellow solid (103.5 mg, 92%),

mp 78-79 oC (lit.24,  73-74.5 oC). 24 J. D. Tovar and T. M. Swager, J. Org. Chem., 1999, 64, 6499

1H NMR (500 MHz, CDCl3) δ 8.25-8.23 (m, 2H), 8.15-8.14 (m, 1H), 8.09 (s, 1H), 7.95-7.93 (m, 1H), 7.84-7.83 (m, 2H), 7.70-7.67 (m, 1H), 7.59-7.50 (m, 6H), 7.44-7.40 (m, 1H);

13C NMR (125 MHz, CDCl3) δ 160.5, 150.3, 140.1, 139.8, 138.0, 130.4, 130.2, 128.8, 128.7, 128.6, 128.4, 127.7, 127.6, 127.2, 127.0, 126.0, 115.8.

//////// isoquinoline, pd-catalyzed, arylboronic acids

A Brønsted acid catalysed enantioselective Biginelli reaction

A Bronsted acid catalysed enantioselective Biginelli reaction

Green Chem., 2017, Advance Article
DOI: 10.1039/C6GC03274E, Paper
Margherita Barbero, Silvano Cadamuro, Stefano Dughera
A chiral derivative of 1,2-benzenedisulfonimide, namely (-)-4,5-dimethyl-3,6-bis(o-tolyl)-1,2-benzenedisulfonimide is herein proven to be an efficient chiral catalyst in a one pot three-component Biginelli reaction.

A Brønsted acid catalysed enantioselective Biginelli reaction

*Corresponding authors
aDipartimento di Chimica, Università di Torino, C.so Massimo d’Azeglio 48, 10125 Torino, Italy
E-mail: stefano.dughera@unito.it
Green Chem., 2017, Advance Article

DOI: 10.1039/C6GC03274E

A chiral derivative of 1,2-benzenedisulfonimide, namely (−)-4,5-dimethyl-3,6-bis(o-tolyl)-1,2-benzenedisulfonimide is herein proven to be an efficient chiral catalyst in a one pot three-component Biginelli reaction. In fact the yields of the target dihydropyrimidines were very high (25 examples; average 91%) and enantiomeric excesses were always excellent (14 examples; average 97%). Ultimately, we herein propose a procedure that displays a number of benefits and advantages including the total absence of solvents, mild reaction conditions, relatively short reaction times and stoichiometric reagent ratios. Target dihydropyrimidines are obtained in adequate purity, making further chromatographic purification unnecessary. Moreover, the chiral catalyst was easily recovered from the reaction mixture and reused, without the loss of catalytic activity.

(R)-(-)-Ethyl 6-methyl-4-phenyl-2-thioxo-3,4-dihydropyrimidine-5-carboxylate (5a): pale grey solid (135 mg, 98% yield); mp 201–202 °C ( from EtOH; lit17 200–202 °C). 96.4% Ee (GC connected to a J&W Scientific Cyclosil-B column; stationary phase: 30% heptakis (2,3-di-Omethyl-6-O-t-butyldimethylsilyl)-β-cyclodextrin in DB-1701), tR= 12.11 min (major), tR= 12.54 min (minor); [a]D -65.4 (c 0.1 in MeOH).

1H NMR (200 MHz, DMSO-d6): δ = 10.24 (br s, 1H), 9.55 (br s, 1H), 7.31–7.12 (m, 5H), 5.09 (d, J = 3.9 Hz, 1H), 3.92 (q, J = 7.0 Hz, 2H), 2.21 (s, 3H), 1.01 (t, J = 7.0 Hz, 3H);

13C NMR (50 MHz, DMSO-d6): δ = 174.9, 165.8, 145.7, 129.3, 128.3, 127.0, 101.3, 60.2, 54.7, 17.8, 14.7.

MS (m/z, EI): 276 [M+ ] (45), 247 (40), 199 (100). IR (neat) ν (cm−1): 3311 (NH), 3112 (NH), 1665 (CO), 1195 (CS).

USES

Image result for Biginelli reaction

Image result for Biginelli reaction

Image result for Biginelli reaction

////////////Bronsted acid,  catalysed, enantioselective, Biginelli reaction