对环芳烷

2.2]对环芳烷类平面手性化合物作为一类崭新的手性配体结构在不对称催化反应中的应用已成为研究热点之一。

[2.2]对环芳烷类配体与二茂铁或羰基金属络合物类平面手性化合物相比，独具以下特点：（1）平面手性的引入较为方便，在其骨架的苯环上只引入一个取代基就可形成平面手性，而在二茂铁或羰基金属络合物中必须至少引入两个不同的取代基才能形成平面手性；（2）这类化合物的基本骨架对光、热、酸、碱、氧化剂以及还原剂等具有高的化学稳定性；（3）骨架不易消旋（一般在200℃附近才会发生消旋化）；（4）由于受分子张力限制，[2.2]对环芳烷具有高刚性，同时，由于[2.2]对环芳烷骨架的一个苯环的对映面被分子中另一苯环所屏蔽，使得手性[2.2]对环芳烷化合物在参与反应时同样有可能提供有效的不对称环境，从而能得到较好的不对称诱导结构。

目前已经有研究者用06-0460（产品编号）这个化合物成功地合成了15-0425、15-0426（产品编号）类双膦配体。该类配体具有以下几个特点：（1）单一平面手性；（2）C2对称性；（3）二苯基膦基处于假邻位（Pseudo-ortho）取代。

15-0425、15-0426（产品编号）类双膦配体是目前[2.2]对环芳烷类平面手性配体中应用最为成功的配体，这类配体在不对称氢化反应中所取得的优秀结构，无疑为[2.2]对环芳烷类平面手性配体在不对称催化反应中的应用展示了良好的发展前景。



06-0104 racemic-4-Bromo[2.2]paracyclophane, min. 95% [1908-61-8]
C16H15Br; FW: 287.19; white pwdr. 500mg
2g
06-0460 racemic-4,12-Dibromo[2.2]paracyclophane, min. 95% [23927-40-4]
C16H14Br2; FW: 366.09; white to off-white pwdr. 250mg
1g
08-0700 racemic-4,12-Dihydroxy[2.2]paracyclophane, min. 97% [612492-27-0]
C16H16O2; FW: 240.30; yellow to brown pwdr. 100mg
500mg
08-2027 racemic-4-Hydroxy[2.2]paracyclophane, min. 97% [157018-15-0]
C16H16O; FW: 224.30; yellow to tan pwdr. 250mg
1g


Paracyclophane-based Ligands and Catalysts
15-0425 (R)-(-)-4,12-Bis(diphenylphosphino)-[2.2]-paracyclophane, min. 95% (R)-PHANEPHOS
C40H34P2; FW: 576.65; white solid; [α]D -62.6° (c 3.11, CH2Cl2); m.p. 222-225°
Note: Sold in collaboration with Chirotech for research purposes only. US Patent no. 5874629.
Technical Note:
1.See 15-0426. 100mg
500mg
15-0426 (S)-(+)-4,12-Bis(diphenylphosphino)-[2.2]-paracyclophane, min. 95% (S)-PHANEPHOS [192463-40-4]
C40H34P2; FW: 576.65; white solid; [α]D +63.2° (c 3.27, CH2Cl2); m.p. 222-225°
Note: Sold in collaboration with Chirotech for research purposes only. US Patent no. 5874629. 100mg
500mg
Technical Notes:
1.Highly enantioselective catalyst for the hydrogenation of dehydroamino acids, methyl esters under mild conditions.
2.Asymmetric hydrogenation of a wide variety of aromatic, heteroaromatic, and α-β unsaturated ketones.

15-0730 (R)-(-)-4,12-Bis(di(3,5-xylyl)phosphino)-[2.2]-paracyclophane, min. 95% CTH-(R)-3,5-xylyl-PHANEPHOS
C48H50P2; FW: 688.86; white pwdr.
Note: Sold in collaboration with JM for research purposes only. US patent Application No 5874629 and patents arising therefrom.
Technical Notes:
1. See 15-0426.
2. See 15-0731. 100mg
500mg
15-0731 (S)-(+)-4,12-Bis(di(3,5-xylyl)phosphino)-[2.2]-paracyclophane, min. 93% CTH-(S)-3,5-xylyl-PHANEPHOS
C48H50P2; FW: 688.86; white pwdr.
Note: Sold in collaboration with JM for research purposes only. US patent Application No 5874629 and patents arising therefrom. 100mg
500mg
Technical Notes:
1. See 15-0426.
2. Chiral ligand employed in the enantioselective hydrogenation of various ketones.

44-0380 Dichloro[(R)-(-)-4,12-bis(di(3,5-xylyl)phosphino)-[2.2]-paracyclophane][(1S,2S)-(-)-1,2-diphenylethylene-diamine]ruthenium (II), min. 95% [325150-57-0]
RuCl2[C48H50P2][C14H16N2]; FW: 1073.12; cream colored pwdr.air sensitive
Note: Sold in collaboration with Chirotech for research purposes only.US Patent nos. 5874629 and 6486337. 10mg
50mg
250mg
Technical Note:
1. These Noyori catalysts containing the chiral xylyl-Phosphane ligands display exceptional activity and enantioselectivity in the asymmetric hydrogenation of a wide range of aromatic,heteroaromatic and α,β-unsaturated ketones. The reactions are performed under mild conditions, and substrate concentrations up to 40%w/v can be tolerated. Molar substrate/catalyst ratios of up to 100,000/l are achieved with excellent reactivity and enantioselectivity using commercial grade substrates and solvents.

44-0381 Dichloro[(S)-(+)-4,12-bis(di(3,5-xylyl)phosphino)-[2.2]-paracyclophane][(1R,2R)-(+)-1,2-diphenylethylene-diamine] ruthenium (II), min. 95%
RuCl2[C48H50P2][C14H16N2]; FW: 1073.12; cream colored pwdr. air sensitive
Note: Sold in collaboration with Chirotech for research purposes only. US Patent nos. 5874629 and 6486337. 10mg
50mg
250mg
Technical Notes:
1.The Noyori [(diphosphine) RuCl2 (diamine)] catalysts containing the chiral ligand Xylyl-Phanephos display exceptionalactivity and enantioselectivity in the asymmetric hydrogenation of a wide range of aromatic, heteroaromatic and α,β-unsaturated ketones.
2.Reactions are performed under mild conditions at room temperature and typically at low H2 pressures of 2-10 bar. Highsubstrate concentrations of up to 40% w/v are tolerated.
3.Molar substrate/catalyst ratios of up to 100,000/1 are achieved with excellent reactivity and enantioselectivity using commercial grade substrates and solvents.

References:
1. Org. Lett., 2000, 2, 4173.
2. Burk, M.J.; Hems, W.; Zanotti-Gerosa, A. PCT WO/0174829 A1, 2001.
3. Org. Proc. Res. Dev., 2003, 7, 89.