First things first, let's get the part about juggles out of the way; After launching an opponent, if you are facing forward, your easiest juggle can simply be PPPK. after launching an opponent and your back is facing them, you want to do BTPP4PP7K (this is actually going to be your BnB juggle universally). My combo video will also demonstrate different launchers and various juggles you can use from each launch height (whether low, mid or high launch heights. These levels will vary depending on critical level threshold 1, 2 and 3, with 3 being the highest);
http://www.freestepdodge.com/threads/hajinshinobis-doa5u-viable-ayane-combo-video.3554/
So when trying to get your damage from juggles, it's best to practice them with and after launching the opponent with different launchers. All demonstrated in the video above, and includes a list of launchers and juggles that were in the video. Should be a good reference.
Now, for situations involving punishment, in DOA, throw punishment is the most generic form of punishment because throws are not breakable in this game, and the frame data working a little differently than other fighting games. This is an exception with neutral throws (neutral throw is done by just pressing throw) and for combo throws that require the aggressor to do additional inputs to complete the combo throw. When Combo Throw appears on the screen, that is when you are prompt to hit the throw button to try and break the throw attempt.
Normally any single strike or string that ends in -8 frame disadvantage is considered throw punishable. Anything from -6 to -7 is considered semi-safe, therefore cannot be truly forward thrown by i7 frame throws. Anything from -1 to -5 is considered safe, where throw attempts become risky since this is not throw punishable on unsafety.
So for the case of trying to punish, it's a good idea to use your forward throw for throw punishment. Let's say you are fighting Hayate, and he does 6PP and you block it. His 6PP is -11 on block, so you're now able to punish him for it by forward throwing him with 6T. Throw punishment has to be done immediately, however, otherwise you risk missing damage and getting hit if you are too late to throw punish. There is indeed strike punishment in this game, but I want to keep it simple for you, for now. Also keep in mind that you're playing a character that has two i7 frame throws for throw punishment, 6T and 4T.
The 4P goes under highs since 4P itself actually has the ability to high crush high strikes, more specifically jabs, jab string attempts, standing neutral kicks, or moves that simply strike high with no mid hitting hitbox.
Here is how you'll want to start practicing on your attempts to open people up in CQC;
Ayane is the not the kind of character who can string herself on someone's block so often, at all. That is fastest way she will lose, instead, her strings work a lot better once you've established a pretty good free cancel/delay game, basically conditioning. In order to do this, you have to learn to get comfortable using and free cancelling things like jab and PP, in conjunction with 2P and Jab/PP from her Back Turned stance. And remembering that jab from Front Turned stance leaves you in Back Turned stance, while BT jab leaves you in Front Turned stance.
Jab and 2P go hand in hand for forcing people to press buttons because it immediately becomes irritating getting poked at often. Your jab is i10 frames and your low jab is i12 frames, so Ayane is one of a few characters with the fastest low in the game, and it's +0 on neutral hit, good reset pressure. As SOON as jab gets blocked, you are -1 with your Back Turned, this is very good because the opponent is always put into a guessing situation from this, always.
Reasons for this are;
1) You can delay jab into PP up to i17 frames without being interrupted by high or mid strikes, you score a counter hit if so, and PP tracks.
2) You have P4P as well which is a high to mid hitting strike that leaves Ayane in Back Turned stance. +0 on neutral hit (+1 at tip range), -5 on block (-4 at tip range), safe. You can delay this string pretty well, up to i21 frames, and even delaying it will catch someone's button press for counter hit stun.
3) Jab puts you BT (Back Turned stance), you have full access to your options from BT stance, including BT T.
4) Things like P > BT8P and P4P > BT8P are very good to mix up often because the opponent cannot react to this since jab makes you respect Ayane on block. P > BT8P can put the fight back at Round 1 Fight neutral space, and can also force people to whiff buttons and let you whiff punish. Or just create space with P > BT8P.
5) You get immediate access to BT6K, which is a frame trap on block +0 (+1 at a little range) and short push back. Your mix up from a blocked BT6K not only allows for strike mix up, but also for Ayane's Integrated Movement as well (1P+K or 7P).
You're basically able to become unpredictable after jab gets blocked since you have tons of options to utilize. And these things will all work out once you practice them and learn to grow comfortable with them. This is the only character in the game that actually gets to create their on block pressure this way so quickly, and safely.
For mid range, the tools I suggest you learn to get comfortable with for now are;
1) 6PK - 6P and 6PK are very good for Ayane and are versatile for both up close and range pokes. 6P is i13 frames and actually has quite a large hitbox so with good spacing, it will stop a lot of approaches from the opponent quite well. 6PK can do the same thing and if it's blocked at a distance, then it is distance safe at -6 and cannot be punished (very good string to help fight at mid range, approach with and even keepout).
2) 3P is one of Ayane's standard range BnB moves, as it serves it's purpose by letting you control space when used right, and a way to keep someone out as well. Has follow ups, one hits mid and can launch on counter hit or Critical Stun threshold. The other hits low and gives +12 frame advantage on neutral hit, or stuns on counter hit and Critical Stun threshold for +25 frame advantage (+18 at fastest stagger escape). 3P is also very good on counter hit and Critical Stun threshold and forces the opponent to guess at a 50/50 because the mid follow up can launch and the low can stun, and you're also able to free cancel and strike another way. 3PP and 3PK are unsafe on block and punishable, so you want to be mindful of this if you're not hitting anything.
3) 3H+K - i19 frame tracking mid kick, covers a lot of distance in front of Ayane and is safe at -3. Bound stun on all hit status, you can see follow ups for 3H+K from my combo video above. This move allows you to control hittable space between you and the opponent really well as long as you space it properly (everything you do at any range will always require good spacing). 3H+K > BT8P is a very good strategy, whether it is blocked or not. Another great thing about this move is that, once it's done, people
always want to try hitting or throwing you for it, which is exactly what you want and is your chance to whiff punish them for trying.
4) 5K - i12 frame tracking high kick, and obviously it has follows with KK. K has very solid range to it, tracks, and it serves as both a great keep out tool, and a range poke. The same is said about BT PK as well, which gives Ayane access to her front turned PPKK string. BT PK also tracks.
5) BT 2K – i18 frame low sweep that tracks while back turned, -12 on block. Leaves Ayane front turned. BT 2K is a very good range poke and keep out tool. It is also range safe. Slightly knocks back on all hit status when at a distance. And stuns on all hit status when up close.
6) BT 3KKK/2K – A series of two low kicks into a mid kick from the BT3 spin. The second option is a series of three low kicks, with the final kick being a true low sweep and guard breaks on block. The entire string tracks, and the mid kick option is unholdable if the second low sweep is hit confirmed. This string is very good because it forces the opponent to hold low (must-hold), because they eat the whole string if they don't. You can also use this string from things like 6P3 and P+KP3/BTP+K3.
For this I would honest suggest just the BT3K though as it is actually very good to poke with at range, and it forces the opponent to crouch and block low. So if you're able to use this comfortable, you can later get adept at applying pressure with it and BT3 itself because it will almost always force the opponent to do something about it.
As for the match with Leon, he has a difficult time approaching Ayane, using what's mentioned above is enough to keep him out (obviously other tools as well). Up close you have all the speed, but simple things like mixing up jab/PP with 2P is always very good to make him do something about it, allowing you dictate the fight up close. I would advise taking Leon into training mode and learning what his strings are so you know what they look like, but definitely pace that so you'll slowly remember his stuff.
As for my stream tutorial, I honestly feel I could have done a lot better with it so I apologize for being sloppy with it. I've already planned to just do a video tutorial and upload it here and to my Youtube this month, so that will actually happen soon.
Hope this helps, if you have any questions you are more than welcome to ask.