作為一種嶄新的手性配體結(jié)構(gòu)，[2.2]對(duì)環(huán)芳烷類平面手性化合物在不對(duì)稱催化反應(yīng)中的應(yīng)用已成為當(dāng)今化學(xué)研究的熱點(diǎn)。

[2.2]對(duì)環(huán)芳烷類配體與二茂鐵或羰基金屬絡(luò)合物類平面手性化合物相比，具有以下特點(diǎn)：（1）平面手性的引入較為方便，在其骨架的苯環(huán)上僅引入一個(gè)取代基即可形成平面手性，而在二茂鐵或羰基金屬絡(luò)合物中必須至少引入兩個(gè)不同的取代基才能形成平面手性；（2）這類化合物的基本骨架對(duì)光、熱、酸、堿、氧化劑以及還原劑等具有很高的化學(xué)穩(wěn)定性；（3）骨架不易消旋（一般在200℃附近消旋化才會(huì)發(fā)生）；（4）由于受分子張力限制，[2.2]對(duì)環(huán)芳烷具有高剛性。同時(shí)，因[2.2]對(duì)環(huán)芳烷骨架的一個(gè)苯環(huán)的對(duì)映面被分子中另一苯環(huán)所屏蔽，使得手性[2.2]對(duì)環(huán)芳烷化合物在參與反應(yīng)時(shí)同樣有可能提供有效的不對(duì)稱環(huán)境，從而能得到較好的不對(duì)稱誘導(dǎo)結(jié)構(gòu)。

目前，已經(jīng)有研究者用06-0460（產(chǎn)品編號(hào)）化合物成功地合成了15-0425、15-0426（產(chǎn)品編號(hào)）類雙膦配體。該類配體具有以下幾個(gè)特點(diǎn)：（1）單一平面手性；（2）C2對(duì)稱性；（3）二苯基膦基處于假鄰位（Pseudo-ortho）取代。

15-0425、15-0426（產(chǎn)品編號(hào)）類雙膦配體是[2.2]對(duì)環(huán)芳烷類平面手性配體中應(yīng)用最為成功的配體，這類配體在不對(duì)稱氫化反應(yīng)中所取得的優(yōu)秀結(jié)構(gòu)，無(wú)疑為[2.2]對(duì)環(huán)芳烷類平面手性配體在不對(duì)稱催化反應(yīng)中的應(yīng)用展現(xiàn)了良好的發(fā)展前景。

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.