Boyd Derek R, Sharma Narain D, Bowers Nigel I, Boyle Rosemary, Harrison John S, Lee Kyoung, Bugg Timothy D, Gibson David T
School of Chemistry, Queen's University of Belfast, Belfast, UK BT9 5AG.
Org Biomol Chem. 2003 Apr 21;1(8):1298-307. doi: 10.1039/b300898c.
Toluene dioxygenase (TDO)-catalysed benzylic hydroxylation of indene substrates (8, 16 and 17), using whole cell cultures of Pseudomonas putida UV4, was found to yield inden-1-ol (14 and 22) and indan-1-one bioproducts (15 and 23). The formation of these bioproducts is consistent with the involvement of carbon-centred radical intermediates. TDO-catalysed oxidation of indenes 8 and 16 also gave cis-diols 13 and 18 respectively. TDO and naphthalene dioxygenase (NDO), used as both whole-cell preparations and as purified enzymes, were found to catalyse the benzylic hydroxylation of chromane 30, deuteriated (+/-)-chromane 30D and enantiomers (4S)-30D and (4R)-30D to yield (4R)- and (4S)-chroman-4-ols 31/31D respectively. The mechanism of benzylic hydroxylation of chromane 30/30D involves the stereoselective abstraction of a pro-R (with TDO) or a pro-S (with NDO) hydrogen atom at C-4 and a marked preference for retention of configuration.
使用恶臭假单胞菌UV4全细胞培养物，发现甲苯双加氧酶（TDO）催化茚底物（8、16和17）的苄基羟基化反应生成茚-1-醇（14和22）和茚满-1-酮生物产物（15和23）。这些生物产物的形成与碳中心自由基中间体的参与一致。TDO催化的茚8和16的氧化反应分别还生成了顺式二醇13和18。发现用作全细胞制剂和纯化酶的TDO和萘双加氧酶（NDO）催化色满30、氘代（±）-色满30D和对映体（4S）-30D和（4R）-30D的苄基羟基化反应，分别生成（4R）-和（4S）-色满-4-醇31/31D。色满30/30D的苄基羟基化反应机制涉及在C-4处对映选择性提取一个前R（对于TDO）或前S（对于NDO）氢原子，并且明显倾向于构型保留。
